Synergistic light and heat stabilizer compositions for synthetic resins and resin compositions containing the same

ABSTRACT

Light and heat stabilizers for synthetic resin compositions and synthetic resin compositions containing such stabilizers are provided, comprising 
     (1) at least one hindered and heterocyclic amine having the formula: ##STR1##  wherein: X is a bivalent linking radical forming with the ring structure ##STR2##  a nitrogen-containing heterocyclic ring having from five to seven ring atoms, preferably piperidine; 
     R 1  and R 2  are each selected from the group consisting of lower alkyl, preferably methyl, and R 1  and R 2  taken together as pentylene (CH 2 ) 5  ; 
     R 3  and R 4  are each selected from the group consisting of lower alkyl, and R 3  and R 4  taken together as one of butylene--(CH 2 ) 4 , pentylene--(CH 2 ) 5 , and CH 2  --C(CH 3 ) 2  --NH--C(CH 3 ) 2  --CH 2  --; 
     n is 1 or 2; and 
     when n is 1, Y is selected from the group consisting of hydrogen, O°, OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and 
     when n is 2, Y is selected from the group consisting of alkylene, alkenylene, alkynylene, cycloalkylene and aralkylene having from one to about thirty carbon atoms; together with 
     (2) at least one alkyl thioalkanoic acid amide having the formula: ##STR3##  wherein: R is alkyl having from about four to about fifty carbon atoms; 
     R&#39; is alkylene having from one to about three carbon atoms; 
     R 8  is selected from the group consisting of hydrogen, alkyl and aryl having from about one to about eighteen carbon atoms; and when n is 2 and p is 0, bivalent alkylene and oxyalkylene linked to N at two positions; 
     R 9  is selected from the group consisting of alkylene, dialkylene, cycloalkylene, and arylene having from about one to about twelve carbon atoms; and isocyanurate; 
     R 10  is selected from the group consisting of alkylene, alkenylene, thiodialkylene and arylene having from about one to about eighteen carbon atoms; 
     m is 1, 2 or 3; 
     n 1  and n 2  are 0, 1 or 2; 
     p, p 1  and p 2  are 0 or 1; 
     and when p is 1, and n and m are each 1, the sum of m, n and p is three; and 
     q 1 , q 2  and q 3  are each 0 or 1: 
     In such combinations, the alkyl thioalkanoic acid amide synergizes the stabilizing effectiveness of the hindered heterocyclic amine.

Hindered 2,2,6,6-tetraalkyl-4-carboxylic acid ester piperidine compounds have been proposed by Murayama et al U.S. Pat. No. 3,640,928 patented Feb. 8, 1972 as light and heat stabilizers for synthetic polymers, such as polyolefins, polyvinyl chloride, polyvinylidene chloride, polyurethanes, and polyamides. These compounds have the general formula: ##STR4## or a salt thereof.

In the above formula:

R₁ and R₂ which may the same or different, each are an alkyl group such as methyl, ethyl, isopropyl or dodecyl, or they form, together with the carbon atom to which they are attached, a saturated alicyclic group such as: ##STR5## or a group of the formula ##STR6## n is an integer of 1 to 3 inclusive: and R₃ is an acyl group.

These compounds have proved to be particularly acceptable because they do not impart a discoloration of their own to the synthetic polymer. The compounds generally employed previously have either been highly colored, such as the nickel compounds (which are normally green) and the 2-hydroxybenzophenones (which are varying shades and intensities of yellow). They also show very little tendency towards sublimation and exudation, and they have an excellent stabilizing action against both heat and light deterioration.

Consequently, the Murayama et al patent has been followed by a large number of patent and literature disclosures by Murayama et al and others of compounds including a 2,2,6,6-tetrasubstituted-4-piperidyl group attached to a base molecule of varying structures.

Murayama et al U.S. Pat. No. 3,898,303 patented Aug. 5, 1975 propose piperidino-spiro-hydrantoin derivatives having the formula: ##STR7## wherein R represents an alkyl group, an alkenyl group, an alkenoylgroup which may be substituted with an aryl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an acyloxyalkyl group, a cyanoalkyl group or nitroso group, and X and Y individually represent oxygen atom or sulfur atom.

Murayama et al in U.S. Pat. No. 3,899,464 patented Aug. 12, 1975 disclose a variation of the piperidino spiro compounds having the formula: ##STR8## wherein R₁ represents hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted aralkyl group, an aliphatic acyl group, an alkoxycarbonyl group or an aralkoxycarbonyl group, n is an integer of 1 to 4;

when n is 1, R₂ represents hydrogen atom, an aliphatic, aromatic or heterocyclic monoacyl group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an alkoxyalkyl group, an epoxyalkyl group, an alkoxysulfonylalkyl group, N-substituted carbamoyl group, a N-substituted thiocarbamoyl group, a monovalent group from an oxoacid or group ##STR9## in which R₃ represents hydrogen atom, a lower alkyl group or phenyl group and R₄ represents an alkyl group;

when n is 2, R₂ represents carbonyl group, an aliphatic or aromatic diacyl group, an alkylene group, an alkenylene group, an alkynylene group, an aralkylene group, a N-substituted dicarbamoyl group or a divalent group from an oxoacid;

when n is 3, R₂ represents an aromatic triacyl group or a trivalent group from an oxoacid; and

when n is 4, R₂ represents an aromatic tetraacyl group, and A represents a group ##STR10## in which R₅ represents hydrogen atom or a lower alkyl group or, when n is 1, R₅ may represent together with R₂ a group ##STR11## in which R₆ represents the same group as defined in R₁ and may be the same or different from R₁, or a group ##STR12## in which m is 1 or 2 and R₇ represents hydrogen atom or, when n and m are 1, R₇ represents methylene group together with R₂.

Murayama et al U.S. Pat. No. 3,840,494, patented Oct. 8, 1974 provides acid esters of 4-piperidinol derivatives having the formula: ##STR13## wherein R₁ and R₂ may be the same or different and represent an alkyl group of one to four carbon atoms or they may form, together with the carbon atom to which they are attached, a saturated alicyclic group or the group of the formula: ##STR14## X is hydrogen atom, oxygen free radical (--O°) or an alkyl group of one to four carbon atoms;

n is an integer of 1 through 4 inclusive; and

R₃ represents,

when n is 1, an acyl group derived from an aliphatic or aromatic monocarboxylic acid,

when n is 2, a diacyl group derived from an aliphatic or aromatic dicarboxylic acid or carbonyl group,

when n is 3, a triacyl group derived from an aliphatic or aromatic tricarboxylic acid or a trivalent group obtained by eliminating three hydroxyl groups from phosphoric acid, phosphorous acid or boric acid, and

when n is 4, a tetraacyl group derived from an aromatic tetracarboxylic acid or a tetravalent group obtained by eliminating four hydroxyl groups from orthosilicic acid.

Murayama et al U.S. Pat. No. 3,933,735 patented Jan. 20, 1976 propose 4-piperidone derivatives having a structure similar to the 4-piperidyl derivatives, but with a keto oxygen at the 4-position of the piperidine ring.

Murayama et al U.S. Pat. No. 3,941,744 patented Mar. 2, 1976, disclose another variation of the piperidino spiro derivatives having the formula: ##STR15## wherein R' represents an alkyl group, a substituted alkyl group, an acyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an amino group, a substituted amino group or nitroso group;

X represents oxygen atom or sulfur atom;

Y represents oxygen atom, sulfur atom or a group of the formula ═N--R" in which R" is hydrogen atom, an alkyl group or a substituted alkyl group;

Z represents oxygen atom or a group of the formula >N--R''' is hydrogen atom, an alkyl group or a substituted alkyl group;

n is an integer of 1 through 4 inclusive; and

R represents, when n is 1, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a substituted phosphino group or a substituted phosphinyl group; when n is 2, an alkylene group, an alkenylene group, an arylene group, a substituted arylene group, an aralkylene group, an alkylenediphenylene group, a bis-(acyloxyalkylene) group, an alkylene-bis-(oxycarbonylalkyl) group, a dialkylene ether group or a diphenylene ether group, when n is 3, an alkanetriyl group, a tris-(acyloxyalkylene) group, an alkane-tris-(oxycarbonylalkyl) group or a group of the group ##STR16## in which p is an integer of 1 through 8 inclusive, and when n is 4, an alkane tetrayl group, a tetrakis-(acyloxyalkylene) group or an alkanetetrakis-(oxycarbonylalkyl) group.

Murayama et al U.S. Pat. No. 3,940,363 patented Feb. 24, 1976 disclose a further variation in which two 2,2,6,6-tetrasubstituted-4-piperidyl groups are linked together via the ring nitrogen atom to an R' alkylene linking group, which may be interrupted with an oxygen or sulfur atom, an alkenylene group, an alkynylene group, an aralkylene group, an aliphatic diacyl group, a group having the formula: ##STR17## in which n is an integer of 1 or 2 and X is an alkylene group, or o-, m- or p-phenylene group or the carbon atoms of CO groups may be directly joined in the absence of X or a group of the formula: ##STR18## in which Y is an alkylene group or o-, m- or p-phenylene group.

Ramey et al U.S. Pat. Nos. 3,875,169 patented Apr. 1, 1975 and 3,991,012 patented Nov. 9, 1976 provide bicyclic hindered amines of the formula: ##STR19## wherein X is H, O, or OH,

n is 1 or 2, and

(a) when n is 1, R is straight-or branched-chain alkyl having one to twenty carbon atoms, phenyl or phenyl substituted by one or more lower alkyl groups, and

(b) when n is 2, R is straight- or branched-chain alkylene having one to twenty carbon atoms, phenylene or phenylene substituted by one or more lower alkyl groups.

Preferred compounds of formula I are those wherein X is H or O; and n is 1 or 2, and

(a) when n is 1, R is n-alkyl having one to twenty atoms, and

(b) when n is 2, R is n-alkylene having one to twelve carbon atoms.

Ramey et al U.S. Pat. Nos. 3,907,803 patented Sept. 23, 1975 and 4,001,181 patented Jan. 4, 1977 provide hindered piperidine carboxamide acids and metal salts thereof of the formula: ##STR20## wherein R₁ and R₂ independently of each other are straight- or branched-chain lower alkyl having one to six carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or substituted with a methyl group,

R₃ is hydrogen, alkyl having one to twelve carbon atoms, β-methoxyethyl alkenyl having three or four carbon atoms, propargyl, benzyl, or alkyl-substituted benzyl,

R₄ is straight- or branched-chain alkylene having one to eight carbon atoms, phenylene, phenylene substituted with one or more alkyl groups, or the group --(CH₂)_(m) Y(CH₂)_(n) --, wherein Y is oxygen or sulfur and m and n independently of each other are an integer of from 1 to 3,

M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, iron, sodium, cobalt, tin, dialkyl tin, and

z has a value of from 1 to 4, the value of z being the same as the available valence of M.

Ramey et al U.S. Pat. Nos. 3,899,491, patented Aug. 12, 1975 and 3,920,659, patented Nov. 18, 1975, disclose alkyl alkanoate derivatives of substituted piperazines and substituted piperazinodiones. The substituted piperazines of No. 3,899,491 have the formula: ##STR21## wherein R¹ and R² are methyl or together with the carbon to which they are bound form a mono-cyclic ring system having five or six carbon atoms;

R³ is an alkyl group of from one to twenty atoms;

R⁴ is hydrogen or methyl, and

m is 0 or 1.

The substituted piperazinodiones of U.S. Pat. No. 3,920,659 have the formula: ##STR22## wherein R¹ and R² are independently of each other methyl or ethyl or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or substituted with a methyl group;

n is an integer of from 1 to 2;

when n is 1, R³ is an alkyl group of from one to twenty carbon atoms;

when n is 2, R³ is an alkylene group of from two to eight carbon atoms; and

A is a straight or branched chain (lower)alkylene group containing from one to six carbon atoms with the limitation that the terminals of said alkylene group bear only hydrogen or one (lower)alkyl group.

Ramey et al U.S. Pat. No. 3,920,661 patented Nov. 18, 1975 disclose dicarboxylic acids and salts in which one carboxylic acid group is esterified with a 2,2,6,6-tetrasubstituted-4-hydroxy piperidine and having the formula: ##STR23## wherein R₁ and R₂ independently of each other are straight- or branched-chain alkyl having from one to six carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or substituted with a methyl group;

R₃ is hydrogen, alkyl having one to twelve carbon atoms, β-methoxyethyl, alkenyl having three or four carbon atoms, propargyl, benzyl or alkyl-substituted benzyl;

R₄ is straight or branched-chain alkylene having five to eight carbon atoms, or the group (CH₂)_(m) Y(CH₂)_(n) wherein Y is oxygen or sulfur and m and n independently of each other are an integer from 1 to 3;

M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, iron, sodium, cobalt, tin, and dialkyl tin, and

z has a value of from 1 to 4, the value of z being the same as the available valence of M.

Ramey et al U.S. Pat. No. 3,939,163 patented Feb. 17, 1976 disclose closely similar compounds in which R₄ is alkylene having from one to four carbon atoms.

Randell et al U.S. Pat. No. 3,939,170 patented Feb. 17, 1976 disclose dehydropyridinyl sulphides, sulphoxides and sulphones having the formula: ##STR24## wherein X is S, SO or SO₂ and Y and Y¹ are the same or different and each is H, OH, O-- or a straight- or branched alkyl residue having from one to four carbon atoms, and salts thereof when Y and Y¹ are other than O--.

Randell et al in published patent application No. B408,123 published Apr. 13, 1976 disclose substituted piperidine-4-ols having the formula: ##STR25## wherein R₁ and R₂ are the same or different and each is a straight- or branched alkyl residue having from one to twelve carbon atoms, or R₁ and R₂, together with the carbon atom to which they are attached, form a cycloalkyl residue having from five to twelve carbon atoms or the group: ##STR26## wherein R₁ and R₂ have their previous significance and Y is a straight- or branched alkyl residue having from one to twenty carbon atoms, an alkenyl or alkynyl residue having from three to twenty carbon atoms, an aralkyl residue having from seven to twelve carbon atoms or the group --CH₂ X wherein X is the group ##STR27## wherein R₃ is hydrogen, a methyl or phenyl residue, the group ##STR28## wherein R₄ is an alkyl residue having from one to twenty carbon atoms.

Cook U.S. Pat. No. 3,929,804 patented Dec. 30, 1975 discloses 4-piperidine acetamide compounds having the formula: ##STR29## wherein R₁ and R₂ are the same or different and each is a straight- or branched alkyl residue having from one to twelve carbon atoms, or R₁ and R₂, together with the carbon atom to which they are attached form a cycloalkyl group having from five to twelve carbon atoms;

R₃ is hydrogen, a straight- or branched alkyl residue having from one to four carbon atoms, an aralkyl residue having from seven to nine carbon atoms or a cycloalkyl group having from five or six carbon atoms;

R₄ is a metal ion or a hydrocarbyl residue having from two to twenty carbon atoms and being either unsubstituted or substituted by halogen or interrupted by one or more oxygen or sulphur atoms;

X is --O--, --S--, or >NR₅, wherein R₅ has the same significance as R₃ ; and

n is 2, 3 or 4;

as well as salts of the amine function of the compounds of formula I.

Cook U.S. Pat. No. 3,939,168 patented Feb. 17, 1976 discloses closely similar compounds having a Y substituent on the piperidyl nitrogen atom, Y being alkyl, alkenyl, aralkyl or a group ##STR30## wherein R₇ is hydrogen, alkyl or phenyl.

Randell et al U.S. Pat. No. 3,939,170, patented Feb. 17, 1976 provides di-4-(3,4-dehydro-2,2,6,6-tetramethyl piperidinyl) sulphides, sulphoxides and sulphones having the formula: ##STR31## wherein X is S, SO or SO₂ and Y and Y¹ are the same or different and each is H, OH, 0° or a straight- or branched-alkyl residue having from one to four carbon atoms, and salts thereof when Y and Y¹ are other than 0°.

Preferably X is S.

Smith et al U.S. Pat. No. 3,954,779, patented May 4, 1976 provides 4-(4'-hydroxycyclohexyl)2,2,6,6-tetramethyl piperidines and derivatives thereof having the formula: ##STR32## and salts thereof, wherein R₁, R₂, R₃ and R₄ are the same or different and each is hydrogen, an alkyl residue having from one to nine carbon atoms, a cycloalkyl residue having from five to fourteen carbon atoms or a cycloalkyl-alkyl residue having from seven to fourteen carbon atoms;

Y is hydrogen;

O an alkyl residue having from one to four carbon atoms, or an aralkyl residue having from seven to twelve carbon atoms; and

Z is hydrogen, an unsubstituted or substituted alkyl residue having from one to twenty carbon atoms, an alkenyl or alkynyl residue having from two to twenty carbon atoms, a cycloalkyl residue having from five to twelve carbon atoms, an aralkyl residue having from seven to twelve carbon atoms, an aryl residue having from six to twelve carbon atoms, or the group having the formula:

    --COZ.sub.1

wherein

Z₁ has the same significance as Z as hereinbefore defined or Z₁ is a group --NR₅ R₆ wherein

R₅ is hydrogen or an alkyl residue having from one to four carbon atoms and

R₆ is hydrogen, an alkyl residue having from one to twenty carbon atoms, a cycloalkyl residue having from five to twelve carbon atoms, an aralkyl residue having from seven to twelve carbon atoms or an aryl residue having from six to twelve carbon atoms.

Cook U.S. Pat. No. 3,959,291, patented May 25, 1976 provides derivatives of substituted 2-piperidinyl-4'-ethyl alcohol having the formula: ##STR33## and salts thereof, wherein R₁ and R₂ are the same or different and each is an alkyl residue having from one to twelve carbon atoms, or R₁ and R₂, together with the carbon atom to which they are bound, form a cycloalkyl residue having from five to twelve carbon atoms in the ring;

Y is O, hydrogen, a straight- or branched-alkyl residue having from one to twenty carbon atoms, an alkenyl or alkynyl residue having from three to twelve carbon atoms, an aralkyl residue having from seven to twelve carbon atoms or a group having the formula: ##STR34## wherein R is hydrogen, or a methyl or phenyl residue, and

R₃ is hydrogen, or a straight- or branched-chain alkyl residue having from one to twelve carbon atoms.

Cook U.S. Pat. No. 3,971,795 patented July 27, 1976 provides N-substituted piperidinylidene derivatives having the formula: ##STR35## wherein n is 1, 2, 3 or 4,

Y is hydrogen or a straight- or branched-alkyl residue having from one to twelve carbon atoms, an alkenyl residue having from three to twelve carbon atoms or an aralkyl residue having from seven to twelve carbon atoms and R₁ and R₂ are the same or different and each is a straight- or branched-alkyl residue having from one to twelve carbon atoms, or R₁ and R₂ together with the carbon atom to which they are attached form a cycloalkyl group having from five to twelve carbon atoms;

R₃ is hydrogen, a straight- or branched-alkyl residue having from one to four carbon atoms, an aralkyl residue having from seven to twelve carbon atoms, a cycloalkyl group having five or six carbon atoms;

R₄ is a hydrocarbyl residue having from one to twenty carbon atoms being either unsubstituted or substituted by halogen, or interrupted by one or more oxygen or sulphur atoms or R₄ is a metal ion, or, when n is 1, R₄, in addition, is hydrogen or has the structure: ##STR36## wherein Y, R₁ and R₂ have their previous significance,

X is --O--, --S-- or >NR₅

wherein

R₅ has the same significance as R₃ or when n is 1 in addition R₅ and R₄ together with the nitrogen atom to which they are bound form a heterocyclic residue having from four to ten carbon atoms;

as well as salts of the amine function of the compound of formula I.

Murayama et al U.S. Pat. No. 3,975,357, patented Aug. 17, 1976 provides 1-substituted piperidine derivatives having the formula: ##STR37##

In the above formula, n represents 1 or 2.

R₁ represents when n=1, oxyl radical, hydroxy group, an alkyl group, a substituted alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a substituted aralkyl group or an acyl group,

when n=2, an alkylene group (the alkylene chain may optionally be interrupted by an oxygen atom), 2-butenylene group, a group of the formula

    --CH.sub.2 COO--R.sub.7 --O--COCH.sub.2 --

wherein

R₇ represents an alkylene group or xylylene group, or a group of the formula

    --CH.sub.2 CH.sub.2 --OCO--R.sub.8).sub.m COO--CH.sub.2 CH.sub.2 --

wherein

m represents 0 or 1,

R₈ represents an alkylene group (the alkylene chain may optionally be interrupted by a sulfur atom), an alkenylene group, phenylene group or 1,4-cyclohexylene group.

R_(a) and R_(b) represent methyl group or R_(a) and R_(b) together with carbon atom to which they are attached, form cyclohexyl group.

R_(c) represents methyl group.

R_(d) represents an alkyl group having one to five carbon atoms.

R_(c) and R_(d) together with carbon atom to which they are attached, may form cyclopentyl group, cyclohexyl group, a group of the formula: ##STR38## or a group of the formula ##STR39##

Murayama U.S. Pat. No. 3,975,462, patented Aug. 17, 1976 provides piperidine-spiro-hydantoin derivatives having the formula: ##STR40##

In the above formula (I), X represents oxygen atom or sulfur atom: n is an integer of 1 to 4 inclusive; and R represents

when n is 1, an alkenyl group which may be substituted with halogen, an alkynyl group which may be substituted with phenyl, an aralkyl group which may be substituted with halogen, alkyl of one to four carbon atoms or halomethyl, a hydroxyalkyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, an aryloxyalkyl group, an alkylthioalkyl group, an acyloxyalkyl group, an epoxyalkyl group, an N-alkyl-substituted aminoalkyl group, an alkoxycarbonyl alkyl group, an aryloxycarbonylalkyl group, an aliphatic acyl group, an alkoxycarbonyl group, a phosphino group which is substituted with phenoxy or alkoxy or a phosphinyl group which is substituted with phenoxy or alkoxy,

when n is 2, an alkenylene group of four to eighteen carbon atoms, a dialkylene ether group, an aralkylene group, a bis-(acyloxyalkylene) group, or an alkylene-bis-(oxycarbonylalkyl) group,

when n is 3, a tris-(acyloxyalkylene) group, an alkane-tris-(oxycarbonylalkyl) group or a group of the formula: ##STR41## in which p is an integer of 1 to 8 inclusive and p's may be the same or different, and,

when n is 4, a tetrakis (acyloxyalkylene) group.

Avar et al U.S. Pat. No. 3,976,658, patented Aug. 24, 1976 provides pyrazole derivatives of the formula: ##STR42## in which R₁ is a C₁₋₂₂ alkyl radical, a C₅₋₁₂ cycloalkyl radical, a C₆₋₁₂ cycloalkylalkyl radical, a C₇₋₂₂ aralkyl radical, of which the alkyl radical and the alkyl moiety of the cycloalkyl-alkyl radical are uninterrupted or interrupted by one or two sulphur atoms or by --COO--, and the aryl nucleus of the aralkyl radical is unsubstituted or substituted by a hydroxyl group and/or 1 or 2 C₁₋₁₂ alkyl radicals, or a phenyl group, unsubstituted or substituted by one or more substituents selected from one to two halogen atoms, a cyano group, a hydroxyl group, 1 or 2 C₁₋₁₂ alkyl radicals, 1 or 2 C₁₋₁₂ alkoxy radicals, a phenyl group and the radicals R₄ --O-- and R₄ --SO₂ --, wherein R₄ is a phenyl group, unsubstituted or substituted by 1 or 2 C₁₋₈ alkyl radicals,

R₂, independently of R₁, has one of the significances of R₁, or is a cyano group or the radical --COOR₅, wherein R₅ is a C₁₋₁₂ alkyl radical, a C₅₋₁₂ cycloalkyl radical, a C₆₋₁₂ cycloalkyl-alkyl radical or a phenyl group, unsubstituted or substituted by a hydroxyl group and/or 1 or 2 C₁₋₈ alkyl radicals.

R₃ is a hydrogen atom or one of the significances of R₁, --COR₁ or --COOR₅,

n is 1, 2 or 3, and

R, when n is 1, is a phenyl group unsubstituted or substituted by a total of up to 3 substituents selected from one hydroxyl group, one to three halogen atoms, one phenyl group, one benzyl group, one phenoxy group, one to three alkyl radicals each containing one to eight carbon atoms and the sum of the carbon atoms not exceeding twelve, and one to three alkoxy radicals each containing one to twenty-two carbon atoms and the sum of the carbon atoms not exceeding twenty-two, or a monovalent naphthalene radical, or a monovalent radical of thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, or dibenzofuran, and

when n is 2, is a phenylene group, unsubstituted or substituted by a C₁₋₄ alkyl radical and/or a halogen atom, or a divalent naphthalene radical, or a divalent radical of thiophene or dibenzofuran, and

when n is 3, is a 1,3,5-trivalent benzene radical.

Murayama et al, U.S. Pat. No. 4,061,616 patented Dec. 6, 1977, provides piperidyl derivatives having the following formula (I) or an acid addition salt thereof: ##STR43## wherein R and R', which may be the same or different, and each represents hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aliphatic or aromatic acyloxyalkyl group, a cyanoalkyl group, a halogenoalkyl group, an epoxyalkyl group, an alkoxycarbonylalkyl group, an aliphatic acyl group, an alkoxycarbonyl group or an aralkoxycarbonyl group.

Murayama U.S. Pat. No. 4,066,615 patented Jan. 3, 1978, provides stabilizers having the formula: ##STR44## wherein: R' represents an alkyl, an acyl, an alkoxycarbonyl, an amino or nitroso group;

Y represents oxygen or sulfur;

Y represents oxygen, sulfur or a group of the formula ═N--R" in which R" is hydrogen or alkyl;

Z represents oxygen or a group of the formula >N--R'" in which R'" is hydrogen or alkyl;

n is an integer of 1 to 4; and

R represents, when n is 1, alkyl, aryl, cycloalkyl, alkoxycarbonyl, substituted phosphino or substituted phosphinyl, when n is 2, alkylene, alkenylene, arylene, aralkylene; alkylenediphenylene, bis-(carboxycarbonyl) alkylene, alkylene-bis-(oxycarbonylalkyl), dialkylene ether or diphenylene ether, when n is 3, alkanetriyl, tris-(alkoxycarbonyl) alkanetriyl, alkanetriyl-tris-(oxycarbonylalkyl) or a group of the formula ##STR45## in which p is an integer of 1 through 8 inclusive, and, when n is 4, alkanetetrayl, tetrakis-(alkoxycarbonyl) alkanetetrayl or alkanetetrayl-tetrakis-(oxycarbonylalkyl).

Soma et al U.S. Pat. No. 4,097,587 patented June 27, 1978 provides 7,7,9,9-tetra-substituted-1,3,8-triazaspiro[4.5]decane-2,4-diones having an alkyl or allyl group at either the 6- or the 10-position which are said to be useful for the stabilization of polymers against photo- and thermal-deterioration.

These compounds have the formula: ##STR46## wherein: R^(a) represents a methyl group;

R^(b) represents a lower alkyl group;

R^(c) represents an alkyl group;

R^(d) represents an alkyl group, a phenyl group or an aralkyl group; or

R^(c) and R^(d), together with the carbon atom to which they are attached, represent a cycloalkyl group;

one of R^(e) and R^(e') represents a hydrogen atom and the other of R^(e) and R^(e') represents a lower alkyl group or an allyl group;

n is 1 or 2;

Y represents a hydrogen atom or, when neither X nor Z represents a hydrogen atom, Y represents a hydrogen atom, a methyl group, an ethyl group, an allyl group or a benzyl group;

X represents a hydrogen atom, an oxyl radical, a lower alkyl group, an alkenyl group, a benzyl group, a 2,3-epoxypropyl group or a group of formula --CH₂ CH₂ OR¹ (wherein R¹ represents a hydrogen atom or an aliphatic, aromatic, araliphatic or alicyclic acyl group);

when n=1:

Z represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group which is unsubstituted or has one or more substituents in its aryl moiety, an aryl group which is unsubstituted or has one or more chlorine and/or methyl substituents, a cyclohexyl group, a 2,3-epoxypropyl group, an alkoxyalkyl group, a phenoxyalkyl group, a group of formula --CH₂ COOR² (wherein R² represents an alkyl group or a phenyl group) or a group of formula ##STR47## (wherein R³ represents a hydrogen atom, a methyl group or a phenyl group, and R⁴ represents a hydrogen atom or an aliphatic, aromatic, araliphatic or alicyclic acyl group);

when n=2:

Z represents an alkylene group, which is optionally interrupted by an oxygen atom, a 2-butenylene group, a xylylene group; an arylene group which is unsubstituted or has one or more methyl substituents, a group of formula ##STR48## (wherein R⁵ represents an oxygen atom or a methylene group), a group of formula --CH₂.COOR⁶ OCO.CH₂ --(wherein R⁶ represents an alkylene group) or a group of formula ##STR49## (wherein R⁷ represents a hydrogen atom, a methyl group or a phenyl group, m is 0 or 1 and R⁸ represents an alkylene group optionally interrupted by a sulphur atom, an alkenylene group, a phenylene group or a 1,4-cyclohexylene group);

and acid addition salts thereof.

Mayer et al U.S. Pat. No. 4,097,452 patented June 27, 1978 provides diazadispiro-hexadecane compounds having the formula: ##STR50## wherein X means ═O, ═NH or ##STR51## R being an alkyl group with 1 to 17 carbon atoms, preferably the methyl group, for the stabilization of organic matter against the decomposition by light and heat.

In accordance with the present invention, light and heat stabilizers for organic polymeric materials are provided, comprising:

(1) at least one hindered and heterocyclic amine having the formula: ##STR52## wherein: X is a bivalent linking radical forming with the ring structure ##STR53## a nitrogen-containing heterocyclic ring having from five to seven ring atoms, preferably piperidine;

R₁ and R₂ are each selected from the group consisting of lower alkyl, preferably methyl, and R₁ and R₂ taken together as pentylene (CH₂)₅ ;

R₃ and R₄ are each selected from the group consisting of lower alkyl, and R₃ and R₄ taken together as one of butylene--(CH₂)₄, pentylene--(CH₂)₅, and CH₂ --C(CH₃)₂ --NH--C(CH₃)₂ --CH₂ --;

n is 1 or 2; and

when n is 1, Y is selected from the group consisting of hydrogen, O°, OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and

when n is 2, Y is selected from the group consisting of alkylene, alkenylene, alkynylene, cycloalkylene and aralkylene having from one to about thirty carbon atoms; together with

(2) at least one alkyl thioalkanoic acid amide having the formula: ##STR54## wherein: R is alkyl having from about four to about fifty carbon atoms;

R' is alkylene having from one to about three carbon atoms;

R₈ is selected from the group consisting of hydrogen, alkyl and aryl having from about one to about eighteen carbon atoms; and when n is 2 and p is 0, bivalent alkylene and oxyalkylene linked to N at two positions;

R₉ is selected from the group consisting of alkylene, thiodialkylene, cycloalkylene, and arylene having from about one to about twelve carbon atoms; and isocyanurate;

R₁₀ is selected from the group consisting of alkylene, alkenylene, thiodialkylene and arylene having from about one to about eighteen carbon atoms;

m is 1, 2 or 3;

n₁ and n₂ are 0, 1 or 2;

p, p₁ and p₂ are 0 or 1;

and when p is 1, n and m are each 1, the sum of m, n and p is three; and

q₁, q₂ and q₃ are each 0 or 1.

In such combinations, the alkyl thioalkanoic acid amide synergizes the stabilizing effectiveness of the hindered heterocyclic amine.

Hindered heterocyclic amine compounds are known to be effective light stabilizers for synthetic resins, and thio ether compounds such as dialkyl thiodipropionate are known to be effective heat stabilizers for synthetic resins. The thio ethers and hindered heterocyclic amine compounds are antagonistic, however, and combinations display a decreased light stability, as compared to ether alone, so combinations thereof are not practical. It is accordingly surprising that the alkylthioalkanoic acid amides do not reduce the light stability, but rather synergize the stabilizing effectiveness of the hindered heterocyclic amine, and at the same time afford good heat stabilizing effectiveness.

A preferred class of the hindered heterocyclic amine compounds is the hindered 2,2,6,6-tetrasubstituted piperidines having one of the formulae: ##STR55## wherein: R₁ and R₂ are each selected from the group consisting of lower alkyl, and R₁ and R₂ taken together as pentylene (CH₂)₅ ;

R₃ and R₄ are each selected from the group consisting of lower alkyl and R₃ and R₄ taken together or as one of butylene--(CH₂)₄, pentylene--(CH₂)₅, and --CH₂ --C(CH₃)₂ --NH--C(CH₃)₂ --CH₂ --;

R₅ and R₆ are selected from the group consisting of hydrogen and lower alkyl;

A is ##STR56## wherein R₇ is lower alkyl; n₁ and n₂ are numbers from 1 to 6; and

Y₁ and Y₂ are selected from the group consisting of hydrogen, O°, OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and

Z₁ and Z₂ are the residue of a carboxylic acid having from one to about thirty carbon atoms or an inorganic oxyacid of phosphorus, silicon, boron or carbon.

Exemplary R,R₁,R₂,R₃,R₄,R₅,R₆, and R₇, Y₁ and Y₂ alkyl in formulae I, Ia, Ib and II are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, n-amyl, isoamyl, tertiary amyl, n-hexyl, isohexyl, secondary hexyl, tertiary hexyl, heptyl, isoheptyl, octyl, tert-octyl, 2-ethyl hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, and octadecyl, and in the case of R₁ also eicosyl, docosyl, tetracosyl, triacontyl, hexatriacontyl, tetracontyl and pentacontyl.

The term "lower alkyl" refers to alkyl having from one to four carbon atoms.

Exemplary R,R₁,R₂,R₃,R₄,R₅,R₆ and R₇, Y₁ and Y₂ alkenyl in formula I, Ia, Ib and II are ethenyl, propenyl, n-butenyl, isobutenyl, tertiary butenyl, secondary butenyl, n-amylenyl, isoamylenyl, tertiary amylenyl, n-hexenyl, isohexenyl, secondary hexenyl, tertiary hexenyl, heptenyl, isoheptenyl, octenyl, tert-octenyl, 2-ethyl hexenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl, and octadecenyl.

Exemplary R,R₁,R₂,R₃,R₄,R₅,R₆,R₇, Y₁ and Y₂ alkynyl in formulae I, Ia, Ib and II are ethynyl, propynyl, n-butynyl, isobutynyl, tertiary butynyl, secondary butynyl, n-amylynyl, isoamylynyl, tertiary amylynyl, n-hexynyl, isohexynyl, secondary hexynyl, tertiary hexynyl, heptynyl, isoheptynyl, octynyl, tert-octynyl, 2-ethyl hexynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, hexadecynyl, and octadecynyl.

Exemplary R,R₁,R₂,R₃,R₄,R₅,R₆ and R₇, Y₁ and Y₂ cycloalkylene in formulae I, Ia, Ib and II include cyclopropylene, cyclobutylene, cycloalkylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, cyclododecylene and cyclooctadecylene.

Exemplary Y₁ and Y₂, R¹,R₉ and R₁₀ alkylene include methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, tertiary butylene, secondary butylene, n-amylene, isoamylene, tertiary amylene, n-hexylene, isohexylene, secondary hexylene, tertiary hexylene, heptylene, isoheptylene, octylene, tert-octylene, 2-ethyl hexylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, hexadecylene, and octadecylene.

Exemplary Y₁ and Y₂ alkynylene include ethynylene, propynylene, isopropynylene, n-butynylene, isobutynylene, tertiary butynylene, secondary butynylene, n-amylynylene, isoamylynylene, tertiary amylynylene, n-hexylynylene, isohexylynylene, secondary hexynylene, tertiary hexynylene, heptynylene, isoheptynylene, octynylene, tert-octynylene, 2-ethyl hexynylene, nonynylene, decynylene, undecynylene, dodecynylene, tridecynylene, tetradecynylene, hexadecynylene and octadecynylene.

Exemplary Y₁ and Y₂ aralkyl and aralkylene include tolyl, tolylene, xylyl, xylylene, mesityl, mesitylene, methylene naphthyl and ethylene naphthyl.

Exemplary Y₁ and Y₂ acyl include acetyl, propionyl, butyroyl, valeroyl, lauroyl, caproyl, capryloyl, oleoyl, stearoyl, palmitoyl, linoleoyl, linolenoyl, ricinoleoyl, and behenoyl.

Exemplary R₉ and R₁₀ aryl include phenyl, naphthyl, benzyl, phenethyl, xylyl, tolyl, mesityl, ethyl phenyl, naphthethyl, and methylnaphthyl.

Exemplary R₉ and R₁₀ arylene include O-, M- and p-phenylene, diphenylene, xylylene, tolylene, and naphthylene.

Exemplary R₁₀ alkenylene include ethenylene, propenylene, butenylene, and pentenylene.

Exemplary R₁₀ thiodialkylene include CH₂ --S--CH₂,CH₂ CH₂ --S--CH₂ CH₂ --, and ##STR57##

Exemplary X bivalent linking radicals include ethylene, CH₂ CH₂, propylene (CH₂)₃, butylene (CH₂)₄, 2,2-dimethyl propylene, 2,2-diethyl propylene, 1,3-dimethyl propylene, 1,2,2,3-tetramethyl propylene and such radicals substituted with aliphatic, aromatic and cycloaliphatic carboxylic acid groups. The X radicals are illustrated in compounds 1 to 98, below.

Exemplary Y₂ radicals include H, O°, OH, methyl, ethyl, propyl, butyl, hexyl, octyl, chloroethyl, hydroxyethyl, epoxypropyl, cyanoethyl, benzyl, phenylethyl, vinyl, allyl, formyl and acetyl.

Exemplary Z₂ carboxylic acids are acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, behenic acid, acrylic acid, methacrylic acid, crotonic acid, oleic acid, linoleic acid, ricinoleic acid, hydroxy acetic acid, amino acetic acid, amino crotonic acid, phenylacetic acid, phenoxy acetic acid, 3,5-di-t-butyl-4-hydroxyphenyl propionic acid, laurylthiopropionic acid, benzoic acid, toluic acid, p-t-butyl-benzoic acid, p-hydroxybenzoic acid, salicylic acid, p-chlorobenzoic acid, p-methoxybenzoic acid, p-nitro-benzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, nicotinic acid, isonicotinic acid, thiophene-2-carboxylic acid, pyroglutamic acid, isonipecotic acid, orotic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid, maleic acid, itaconic acid, acetylene dicarboxylic acid, bis-(3,5-di-t-butyl-4-hydroxybenzyl) malonic acid, thiodipropionic acid, thiodiglycolic acid, methylene bis thioglycolic acid, iminodiacetic acid, tartaric acid, malic acid, thiomalic acid, dihydroxy tartaric acid, epoxy succinic acid, 3,4-di-hydroxy thiophene dicarboxylic acid, 1,4-bis-carboxyethyl piperidine, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 5-bicyclo-(2,2,1)heptene-2,3-dicarboxylic acid, 5-bicyclo(2,2,2)heptene-2,3-dicarboxylic acid, propane tricarboxylic acid, butane tricarboxylic acid, butene tricarboxylic acid, nitrilo triacetic acid, citric acid, tris carboxyethyl isocyanurate, tris carboxymethyl isocyanurate, trimellitic acid, butane tetracarboxylic acid, ethylene tetracarboxylic acid, ethylene diamine tetracarboxylic acid, pyromellitic acid, 1,3-bis-(aminomethyl) cyclohexane-N,N,N',N'-tetraacetic acid.

Exemplary inorganic Z₂ oxyacids are phosphorous acid, phosphoric acid, phosphonic acid, phosphonous acid, alkyl phosphonic acids, alkyl phosphonous acids, silicic acid, dialkyl silicic acid, boric acid, and carbonic acid.

The Z₂ acid residue may be substituted by ester groups COOR₈ wherein R₈ is alkyl, cycloalkyl or aryl having from one to about thirty carbon atoms.

Two Z₂ ester groups can include spiro groups of the formula ##STR58## wherein m₁ is a number from 0 to 2;

m₂ is a number from 1 to 10;

Y₃ is a spiro linking group selected from alkylene and alkylidene, arylene, cycloalkylene and aralkylene having from one to about ten carbon atoms, and ##STR59## is the polyhydric alcohol or phenol from which such groups are derived; and

Z₃,Z₄,Z₅,Z₆,Z₇,Z₈ and Z₉ are as Z₂, above.

Exemplary such polyhydric alcohols are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, thiodiethylene glycol, 1,6-hexanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-phenyldimethanol, hydrogenated bis-phenol A, glycerine, trimethylolethane, trimethylolpropane, tris-(2-hydroxyethyl) isocyanurate, pentaerythritol, neopentyl glycol, sorbitol, mannitol, erythritol and dulcitol.

Exemplary such polyhydric phenols are hydroquinone, 4,4'-isopropylidene diphenol, 4,4'-cyclohexylidene diphenol, 4,4'-methylene bisphenol, 4,4'-sulfobisphenol, 2,5-di-t-butyl hydroquinone, trimethylhydroquinone, 2-methyl resorcinol, 2,2'-methylene bis-(4-methyl-6-t-butyl phenol), 2,2'-methylene bis-(4-ethyl-6-t-butylphenol), 2,2'-methylene bis-[4-methyl-6-(α-methyl cyclohexyl)phenol], 2,2'-n-butylidene bis-(4,6-di-methyl phenol), bis-1,1-(2'-hydroxy-3',5'-dimethyl phenyl)-3,5,5-trimethyl hexane, 2,2'-cyclohexylidene bis-(4-ethyl-6-t-butyl phenol), 2,2'-thio bis-(4-t-butyl-6-methyl phenol), 2,2'-thio bis-(4-methyl-6-t-butyl phenol), 2,2'-thio bis-(4,6-di-t-butyl phenol), 4,4'-methylene bis-(2-methyl-6-t-butyl phenol), 4,4'-isopropylidene bis-(2-phenyl ethyl phenol), 4,4'-n-butylidene bis-(3-methyl-6-t-butyl phenol), 4,4'-cyclohexylidene bis-(2-t-butyl-phenol), 4,4'-cyclohexylidene bis-(2-cyclohexyl phenol), 4,4'-benzylidene bis-(2-t-butyl-5-methyl phenol), 4,4'-oxo bis-(3-methyl-6-isopropyl phenol), 4,4'-thio bis-(2-methyl-6-t-butylphenol), 4,4'-thio bis-(3-methyl-6-t-butyl phenol), 4,4'-sulfo-bis-(3-methyl-6-t-butyl phenol), bis-(2-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butyl phenyl) butane, 2,2-bis-(3'-t-butyl-4'-hydroxy phenyl)-4-(3",5"-di-t-butyl-4"-hydroxy phenyl)butane, etc.

Preferred subclasses of compounds falling within Formula I and examples thereof are as follows:

    __________________________________________________________________________      ##STR60##                                                                     No.  Y.sub.3     Z'.sub.3                                                      __________________________________________________________________________     1.   H                                                                                           ##STR61##                                                    2.   H                                                                                           ##STR62##                                                    3.   H           OCOC.sub.7 H.sub.15 (n)                                       4.   H           OCOC.sub.17 H.sub.35 (n)                                      5.   H                                                                                           ##STR63##                                                    6.   H                                                                                           ##STR64##                                                    7.   CH.sub.3                                                                                    ##STR65##                                                    8.   CH.sub.3                                                                                    ##STR66##                                                    9.   CH.sub.3    OCOC.sub.17 H.sub.35 (n)                                      10.  CH.sub.3                                                                                    ##STR67##                                                    11.  H                                                                                           ##STR68##                                                    12.  H                                                                                           ##STR69##                                                    13.  H                                                                                           ##STR70##                                                    14.  CH.sub.3                                                                                    ##STR71##                                                    15.  C.sub.3 H.sub.7                                                                            OCOC.sub.7 H.sub.15 (n)                                       16.  CH.sub.2 CHCH.sub.2                                                                        OCOC.sub.7 H.sub.15 (n)                                       17.  H                                                                                           ##STR72##                                                    18.  H           NHCOCHCH.sub.2                                                19.  H           NHCOC.sub.17 H.sub.35 (n)                                     20.  H                                                                                           ##STR73##                                                    21.  H                                                                                           ##STR74##                                                    28.  H                                                                                           ##STR75##                                                    39.  H                                                                                           ##STR76##                                                    40.  CH.sub.3                                                                                    ##STR77##                                                    41.  H                                                                                           ##STR78##                                                    42.  H           OCH.sub.2 CH.sub.2 CN                                         43.  CH.sub.3                                                                                    ##STR79##                                                    46.  H                                                                                           ##STR80##                                                    47.  CH.sub.3                                                                                    ##STR81##                                                    48.  H                                                                                           ##STR82##                                                    49.  H                                                                                           ##STR83##                                                    50.  H                                                                                           ##STR84##                                                    51.  H                                                                                           ##STR85##                                                    52.  H                                                                                           ##STR86##                                                    61.  n-C.sub.8 H.sub.17                                                                         H                                                             62.  n-C.sub.12 H.sub.25                                                                        H                                                                   ##STR87##  H                                                                   ##STR88##  H                                                             65.  O.sup.•                                                                               ##STR89##                                                    66.  O.sup.•                                                                               ##STR90##                                                    67.  H                                                                                           ##STR91##                                                    68.  H                                                                                           ##STR92##                                                    69.  H                                                                                           ##STR93##                                                    70.  H                                                                                           ##STR94##                                                    71.  H                                                                                           ##STR95##                                                    72.  H                                                                                           ##STR96##                                                    74.  H                                                                                           ##STR97##                                                    75.  H                                                                                           ##STR98##                                                    76.  H                                                                                           ##STR99##                                                    77.  H                                                                                           ##STR100##                                                   79.  H                                                                                           ##STR101##                                                   81.  H                                                                                           ##STR102##                                                   83.  H                                                                                           ##STR103##                                                   84.  H                                                                                           ##STR104##                                                   85.  H                                                                                           ##STR105##                                                   87.  H                                                                                           ##STR106##                                                   89.  H                                                                                           ##STR107##                                                   90.  H                                                                                           ##STR108##                                                   91.  H                                                                                           ##STR109##                                                   92.  H                                                                                           ##STR110##                                                   94.  H                                                                                           ##STR111##                                                   95.  H                                                                                           ##STR112##                                                   98.  CH.sub.3                                                                                    ##STR113##                                                   __________________________________________________________________________      ##STR114##                                                                    No.        Z.sub.4'      No.        Z.sub.4'                                   __________________________________________________________________________                 ##STR115##   53.                                                                                        ##STR116##                                44.        NOH           54.                                                                                        ##STR117##                                            ##STR118##                                                         __________________________________________________________________________      ##STR119##                                                                    No. Y.sub.4                                                                            X.sub.4                                                                            B         No. Y.sub.4                                                                              X.sub.4                                                                            B                                          __________________________________________________________________________     23. H   H                                                                      n-C.sub. 4 H.sub.9                                                                 35. CH.sub.3                                                                           CH.sub.3                                                                                  ##STR120##                                              24. CH.sub.3                                                                           H                                                                      n-C.sub. 4 H.sub.9                                                                 36. CH.sub.3                                                                           H         H                                                        25. H   H                                                                      n-C.sub. 8 H.sub.17                                                                37. C.sub.6 H.sub.5 CH.sub.2                                                           H                                                                  n-C.sub. 8 H.sub.17                                                            26. CH.sub.3                                                                           H                                                                      n-C.sub. 8 H.sub. 17                                                           27. H   H   CH.sub.2CHCH.sub.2                                                 29. H   H                                                                                   ##STR121##                                                        30. CH.sub.3                                                                           H                                                                                   ##STR122##                                                        31. H   H   C.sub.18 H.sub.37                                                  32. H   H                                                                                   ##STR123##                                                        33. CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                           34. CH.sub.3                                                                           CH.sub.3                                                                            ##STR124##                                                        __________________________________________________________________________      ##STR125##                          E. Miscellaneous                          No.                                                                               R.sub.8                                                                           p Z.sub.5'                    No.                                        __________________________________________________________________________        C.sub.2 H.sub.5                                                                   2                                                                                 ##STR126##                 38.                                                                                ##STR127##                                C.sub.2 H.sub.5                                                                   2                                                                                 ##STR128##                 55.                                                                                ##STR129##                             80.                                                                               CH.sub.3                                                                          4                                                                                 ##STR130##                 56.                                                                                ##STR131##                                H  6                                                                                 ##STR132##                 57.                                                                                ##STR133##                                C.sub.2 H.sub.5                                                                   4                                                                                 ##STR134##                 58.                                                                                ##STR135##                                C.sub.2 H.sub.5                                                                   2                                                                                 ##STR136##                 59.                                                                                ##STR137##                                C.sub.2 H.sub.5                                                                   2                                                                                 ##STR138##                 60.                                                                                ##STR139##                                CH.sub.3                                                                          2                                                                                 ##STR140##                                                            __________________________________________________________________________

The names of the above-listed compounds falling within Formula I are as follows:

1. 4-Benzoyloxy-2,2,6,6-tetramethyl piperidine

2. 4-Salicyloyloxy-2,2,6,6-tetramethyl piperidine

3. 4-Capryloyloxy-2,2,6,6-tetramethyl piperidine

4. 4-Stearoyloxy-2,2,6,6-tetramethyl piperidine

5. 4-(β-3,5-Di-t-butyl-4-hydroxyphenyl propionyloxy)-2,2,6,6-tetramethyl piperidine

6. 4-(3,5-Di-t-butyl-4-hydroxy benzoyloxy)-2,2,6,6-tetramethyl piperidine

7. 4-Benzoyloxy-1,2,2,6,6-pentamethyl piperidine

8. 4-Salicyloyloxy-1,2,2,6,6-pentamethyl piperidine

9. 4-Stearoyloxy-1,2,2,6,6-pentamethyl piperidine

10. 4-t-Butyl benzoyloxy-1,2,2,6,6-pentamethyl piperidine

11. Bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate

12. Bis-(2,2,6,6-tetramethyl-4-piperidinyl) suberate

13. Bis-(2,2,6,6-tetramethyl-4-piperidinyl) decanedicarboxylate

14. Bis-(1,2,6,6-pentamethyl-4-piperidinyl) sebacate

15. 4-Capryloyloxy-1-propyl-2,2,6,6-tetramethyl piperidine

16. 4-Capryloyloxy-1-allyl-2,2,6,6-tetramethyl piperidine

17. 4-Benzoylamino-2,2,6,6-tetramethyl piperidine

18. 4-Acryloylamino-2,2,6,6-tetramethyl piperidine

19. 4-Stearoylamino-2,2,6,6-tetramethyl piperidine

20. N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl) oxalamide

21. N-(2,2,6,6-tetramethyl-4-piperidinyl) cyclohexanone-imine

22. (2,2,6,6-Tetramethyl piperidine-4-one)azine

23. 3-n-Butyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

24. 3-n-Butyl-8-methyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

25. 3-n-Octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

26. 3-n-Octyl-8-methyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

27. 3-Allyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane 2,4-dione

28. Tetra-(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-bis-(aminomethyl) cyclohexane tetraacetate

29. 3-Glycidyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

30. 3-Glycidyl-8-methyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

31. 3-Octadecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

32. 3-Cyclohexyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

33. 1,3,8-Trimethyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

34. 1,8-Dimethyl-3-hexamethylene-bis-(7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione)

35. 1,8-Dimethyl-3-(3-oxapentamethylene)-bis-(7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione)

36. 7,7,8,9,9-Pentamethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

37. 3-n-Octyl-8-benzyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione

38. 1,3,8-Triaza-2-n-undecyl-4-oxo-7,7,9,9-tetramethylspiro[4,5]decane

39. 2,4,6-Tris-(2,2,6,6-tetramethyl-4-piperidinyloxy)-s-triazine

40. 2,4,6-Tris-(1,2,2,6,6-pentamethyl-4-piperidinyloxy)-s-triazine

41. 2,4,6-tris-(2,2,6,6-tetramethyl-4-piperidinylamino)-s-triazine

42. 2,2,6,6,-Tetramethyl-4-β-cyanoethoxy piperidine

43. 1,2,2,6,6-Pentamethyl-4-lauroyloxy piperidine

44. Triacetone amine-oxime

45. Ethyl-(2,2,6,6-tetramethyl piperidinylidene-4)-acetate

46. Stearyl-(2,2,6,6-tetramethyl piperidinyl-4)-acetate

47. Ethyl-(1,2,2,6,6-pentamethyl piperidinyl-4)-acetate

48. 2,2,6,6-Tetramethyl-4-piperidinyl (2,2,6,6-tetramethyl piperidinyl-4) acetate

49. N,N'-bis(2,2,6,6-tetramethyl piperidinyl-4-acetyl) ethylenediamine

50. 2,2,6,6-Tetramethyl-4-(β-capryloylaminoethyl) piperidine

51. N,N'-bis-β-(2,2,6,6-tetramethyl piperidinyl-4)-ethyl oxalamide

52. 2,6-Dimethyl-4-(2,2,6,6-tetramethyl piperidinyl-4)-phenol

53. Bis-(2,2,6,6-tetramethyl piperidinyl-4) adipoyl hydrazone

54. 2,2,6,6-Tetramethyl piperidinyl-4-capryloyl hydrazone

55. 2,2,7,7-Tetramethyl-hexahydro-5H-1,4-diazepin-5-one

56. 5,5,7,7-Tetramethyl piperidino[5,4-0]-Δ³ -thiazoline-2-spiro-4-(2,2,6,6-tetramethyl piperidine)

57. Cyclohexane-1-spiro-2'-(4'-oxoimidazoline)-5'-spiro-1"-cyclohexane

58. 7,15-Diazadispiro[5,1,5,3]hexadecane

59. 4-n-Octadecyl-2,2,6,6-tetramethyl-3,5-diketo piperazine

60. 15,15'-Sebacoyl-bis-(7,15-diazadispiro[5,15,3]hexadecane)

61. 1-n-Octyl-2,2,6,6-tetramethyl piperidine

62. 1-n-Dodecyl-2,2,6,6-tetramethyl piperidine

63. 1-β-Stearoyloxyethyl-2,2,6,6-tetramethyl piperidine

64. 1-n-Octoxy carbonylmethyl-2,2,6,6-tetramethyl piperidine

65. 2,2,6,6-Tetramethyl-4-benzoyl piperidine-1-oxyl

66. Bis-(2,2,6,6-tetramethyl-4-piperidinyl-1-oxyl) sebacate

67. Tris-(2,2,6,6-tetramethyl-4-piperidinyl) nitrilo triacetate

68. Tris-(2,2,6,6-tetramethyl-4-piperidinyl) butane tricarboxylate

69. Tetra-(2,2,6,6-tetramethyl-4-piperidinyl) butane tetracarboxylate

70. Tris-(2,2,6,6-tetramethyl-4-piperidinyl) trimellitate

71. Tetra-(2,2,6,6-tetramethyl-4-piperidinyl) pyromellitate

72. Bis-(2,2,6,6-tetramethyl-4-piperidinyl) terephthalate

73. Bis-(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5,5]-3-undecylmethyl) methyl iminodiacetate

74. Tris-(2,2,6,6-tetramethyl-4-piperidinyl) citrate

75. Tris-(2,2,6,6-tetramethyl-4-piperidinyl) phosphite

76. Bis-(2,4-di-t-butylphenyl)-2,2,6,6-tetramethyl-4-piperidinyl phosphite

77. Bis-(2,2,6,6-tetramethyl-4-piperidinyl) pentaerythritol diphosphite

78. Bis-(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5,5]-3-undecylmethyl).pentaerythritol.diphosphite

79. Tetra-(2,2,6,6-tetramethyl-4-piperidinyl).bisphenol A.diphosphite

80. Tetra-(9-aza-8,8,10,10-tetramethyl-3-methyl-1,5-dioxaspiro[5,5]-3-undecylmethyl).4,4'-butylidene bis-(2-t-butyl-5-methyl phenol).diphosphite

81. Tetra-(2,2,6,6-tetramethyl-4-piperidinyl).1,6-hexane diol.diphosphite

82. Hexa-(9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5,5]-3-undecylmethyl).1,1,3-tris-(2-methyl-4-hydroxy.5-t-butylphenyl) butane.triphosphite.

83. Hexa-(2,2,6,6-tetramethyl-4-piperidinyl).tris-(2-hydroxyethyl) isocyanurate.triphosphite

84. Tetra-(2,2,6,6-tetramethyl-4-piperidinyl).neopentyl glycoldiphosphite

85. Tetra-(2,2,6,6-tetramethyl-4-piperidinyl).hydrogenated bisphenol A.diphosphite

86. Tetra-(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5,5]-3-undecylmethyl).hydrogenated bisphenol A.diphosphite

87. Tris-(2,2,6,6-tetramethyl-4-piperidinyl) phosphate

88. Bis-(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5,-dioxaspiro[5,5]-3-undecylmethyl).pentaerythritol.diphosphite

89. 3,5-Di-t-butyl-4-hydroxybenzyl-bis-(2,2,6,6-tetramethyl-4-piperidiyl) phosphonate

90. Phenyl-bis-(2,2,6,6-tetramethyl-4-piperidinyl) phosphinate

91. Tris-(2,2,6,6-tetramethyl-4-piperidinyl) borate

92. Bis-(2,2,6,6-tetramethyl-4-piperidinyl) dimethyl silicate

93. Bis-(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5,5]-3-undecylmethyl) carbonate

94. Bis-(2,2,6,6-tetramethyl-4-piperidinyl) carbonate

95. Bis-(2,2,6,6-tetramethyl-4-piperidinyl).4,4'-butylidene bis-(2-t-butyl-5-methylphenol).dicarbonate

96. Bis-(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5,5]-3-undecylmethyl).hydrogenated bisphenol A.dicarbonate

97. Bis-(9-aza-8,8,10,10-tetramethyl-3-methyl-1,5-dioxaspiro[5,5]-3-undecylmethyl).ethylene glycol.dicarbonate

98. Bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-ditertiarybutyl-4-hydroxybenzyl) malonate.

These compounds are known compounds and their preparation is described in the literature.

The alkylthioalkanoic acid amides of formula (II) are also for the most part known compounds, and are readily prepared by conventional procedures.

Tokuno et al Japanese Pat. No. 16,286/68 describes the compounds of the formula: ##STR141##

Ozeki et al Japanese Pat. No. 20,366/68 describes the compounds of the formula: ##STR142##

Yamamoto et al Japanese Pat. No. 23,765/68 describes the compounds of the formula:

    R--S--C.sub.2 H.sub.4 --CONHNHCO--C.sub.2 H.sub.4 --S--R

Ozeki et al Japanese Pat. No. 26,184/69 describes the compounds of the formula:

    R--S--C.sub.2 H.sub.4 --CO--NHNH--CO--R.sub.1 --CO--NHNH--CO--C.sub.2 H.sub.4 --S--R

Ozeki Japanese Pat. No. 31,464/69 describes compounds of the formula:

    R--S--C.sub.2 H.sub.4 --CONH--CH.sub.2 --NHCO--C.sub.2 H.sub.4 --S--R

Minagawa et al Japanese Kokai No. 106,484/74 describes the compounds of the formula:

    R--S--C.sub.2 H.sub.4 CO--NHNH--COCO--NHNH--COC.sub.2 H.sub.4 --S--R

The sulfur-containing amides having the formula: ##STR143## are novel. R₁ is alkyl having from one to fifty carbon atoms or the group --R₂ --COO--R₄ ;

R₂ is alkylene having from one to three carbon atoms;

R₃ is alkylene having from two to twelve carbon atoms; and

R₄ is alkyl having from one to fifty carbon atoms.

The following Example Illustrates the procedure for preparing these compounds:

EXAMPLE A

28.8 g of methyl.lauryl thiopropionate and 3.0 g of ethylene diamine were dissolved in 50 ml of ethanol and refluxed for seven hours.

The solvent was distilled off. Crystallization of the residue from methanol yielded 17.5 g of white scaly crystalline material, m p 136° C.

I.R.: νNH=3300 cm⁻¹, νC=O=1640 cm⁻¹

Analysis for C₃₂ H₆₄ N₂ S₂ O₂ : Calculated: C, 67.1; H, 11.2; N, 4.9; S, 11.2; O, 5.6. Found: C, 66.9; H, 113; N, 5.1; S, 11.1; O, 5.6.

The analysis demonstrated that the compound had the formula:

    C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--C.sub.2 H.sub.4 --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25

Exemplary amines of the type (R₈)_(n) --N--(H)_(3-n) where n is 1, 2 or 3, include ammonia, methylamine, ethylamine, isopropylamine, octylamine, dodecylamine, octadecylamine, monoethanolamine, diethanolamine, triethanolamine, aniline, naphthylamine, diethylamine, morpholine, piperidine, hydrazine, phenylhydrazine, methylhydrazine, methylene diamine, ethylene diamine, cyclohexanediamine, bis(aminomethyl)cyclohexane, phenylene diamine, piperazine, diethylenetriamine, hexahydrotriazine and diphenylenetriamine.

Exemplary polycarboxylic acids of the type HOOCR₁₀ COOH are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, thiodipropionic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, ethylene tetracarboxylic acid, pyromellitic acid, tetrahydrophthalic acid, and 5-bicyclo[2,2,1]heptene-2,3-di-carboxylic acid.

Typical examples of alkyl thioalkanoic acid amide compounds are as follows: ##STR144##

In addition to the light and heat stabilizer combinations of the invention, other conventional stabilizers can be included, such as phenolic antioxidant heat stabilizers, and similar adjuncts.

The phenolic antioxidant contains one or more phenolic hydroxyl groups, and one or more phenolic nuclei, and can contain from about eight to about three hundred carbon atoms. In addition, the phenolic nucleus can contain an oxy or thio ether group.

The alkyl-substituted phenols and polynuclear phenols, because of their molecular weight, have a higher boiling point, and therefore are preferred because of their lower volatility. There can be one or a plurality of alkyl groups of one or more carbon atoms. The alkyl group or groups including any alkylene groups between phenol nuclei preferably aggregate at least four carbon atoms. The longer the alkyl or alkylene chain, the better the compatibility with polypropylene, inasmuch as the phenolic compound then acquires more of an aliphatic hydrocarbon character, and therefore there is no upper limit on the number of alkyl carbon atoms. Usually, from the standpoint of availability, the compound will not have more than about eighteen carbon atoms in an alkyl, alicyclidene and alkylene group, and a total of not over about fifty carbon atoms. The compounds may have from one to four alkyl radicals per phenol nucleu.

The phenol contains at least one and preferably at least two phenolic hydroxyls, the two or more hydroxyls being in the same ring, if there is only one. In the case of bicyclic phenols, the rings can be linked by thio or oxyether groups, or by alkylene, alicyclidene or arylidene groups.

The monocyclic phenols which can be employed have the structure: ##STR145##

R is selected from the group consisting of hydrogen; halogen; and organic radicals containing from one to about thirty carbon atoms, such as alkyl, aryl, alkenyl, alkaryl, aralkyl, cycloalkenyl, cycloalkyl, alkoxy, and acyl ##STR146## where R' is aryl, alkyl or cycloalkyl.

x₁ and x₂ are integers from one to four, and the sum of x₁ and x₂ does not exceed six.

The polycyclic phenol is one having at least two aromatic nuclei linked by a polyvalent linking radical, as defined by the formula: ##STR147## wherein Y is a polyvalent linking group selected from the group consisting of oxygen; carbonyl; sulfur; sulfinyl; aromatic, aliphatic and cycloaliphatic hydrocarbon groups; and oxyhydrocarbon, thiohydrocarbon and heterocyclic groups. The linking group can have from one to twenty carbon atoms.

Ar is a phenolic nucleus which can be a phenyl or a polycarboxylic group having condensed or separate phenyl rings; each Ar group contains at least one free phenolic hydroxyl group up to a total of five. The Ar rings can also include additional rings connected by additional linking nuclei of the type Y, for example, Ar--Y--Ar--Y--Ar.

m₁ and m₂ are numbers from one to five, and n₁ and n₂ are numbers of one or greater, and preferably from one to four.

The aromatic nucleus Ar can, in addition to phenolic hydroxyl groups, include one or more inert substituents. Examples of such inert substituents include hydrogen, halogen atoms, e.g. chlorine, bromine and fluorine; organic radicals containing from one to about thirty carbon atoms, such as alkyl, aryl, alkaryl, aralkyl, cycloalkenyl, cycloalkyl, alkoxy, aryloxy and acyloxy ##STR148## where R' is aryl, alkyl or cycloalkyl, or thiohydrocarbon groups having from one to about thirty carbon atoms, and carboxyl ##STR149## groups. Usually, however, each aromatic nucleus will not have more than about eighteen carbon atoms in any hydrocarbon substituent group. The Ar group can have from one to four substituent groups per nucleus.

Typical aromatic nuclei include phenyl, naphthyl, phenanthryl, triphenylenyl, anthracenyl, pyrenyl, chrysenyl, and fluorenyl groups.

When Ar is a benzene nucleus, the polyhydric polycyclic phenol has the structure: ##STR150## wherein R₁, R₂ and R₃ are inert substituent groups as described in the previous paragraph;

m₁ and m₃ are integers from one to a maximum of five;

m₂ is an integer from one to a maximum of four;

x₁ and x₃ are integers from zero to four, and

x₂ is an integer from zero to three;

y₁ is an integer from zero to about six and

y₂ is an integer from one to five, preferably one to two.

Preferably, the hydroxyl groups are located ortho and/or para to Y.

Exemplary Y groups are alkylene, alkylidene, and alkenylene arylene, alkyl arylene, arylalkylene, cycloalkylene, cycloalkylidene, and oxa- and thia-substituted such groups; carbonyl groups, tetrahydrofuranes, esters and triazino groups. The Y groups are usually bi, tri, or tetravalent, connecting two, three or four Ar groups. However, higher valency Y groups, connecting more than four Ar groups can also be used. According to their constitution, the Y groups can be assigned to subgenera as follows:

(1) Y groups where at least one carbon in a chain or cyclic arrangement connect the aromatic groups, such as: ##STR151##

(2) Y groups where only atoms other than carbon link the aromatic rings, such as ##STR152## where x is a number from one to ten;

(3) Y groups made up of more than a single atom including both carbon and other atoms linking the aromatic nuclei, such as: ##STR153##

Although the relation of effectiveness to chemical structure is insufficiently understood, many of the most effective phenols have Y groups of subgenus (1), and accordingly this is preferred. Some of these phenols can be prepared by the alkylation of phenols or alkyl phenols with polyunsaturated hydrocarbons such as dicyclopentadiene or butadiene.

Representative phenols include guaiacol, resorcinol monoacetate, vanillin, butyl salicylate, 2,6-di-tert-butyl-4-methyl phenol, 2-tert-butyl-4-methoxy phenol, 2,4-dinonyl phenol, 2,3,4,5-tetradecyl phenol, tetrahydro-α-naphthol, o-, m- and p-cresol, o-, m- and p-phenylphenol, o-, m- and p-xylenols, the carvenols, symmetrical xylenol, thymol, o-, m- and p-nonylphenol, o-, m- and p-dodecyl-phenol, and o-, m- and p-octyl-phenol, o-, and m-tert-butyl-p-hydroxy-anisole, p-n-decyloxy-phenol, p-n-decyloxy-cresol, nonyl-n-decyloxy-cresol, eugenol, isoeugenol, glyceryl monosalicylate, methyl-p-hydroxycinnamate, 4-benzyloxy-phenol, p-acetylaminophenol, p-stearyl-aminophenol methyl-p-hydroxybenzoate, p-di-chlorobenzyl-aminophenol, p-hydroxysalicyl anilide, stearyl-(3,5-di-methyl-4-hydroxy-benzyl)thioglycolate, stearyl-β-(4-hydroxy-3,5-di-t-butylphenyl)propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, and distearyl(4-hydroxy-3-methyl-5-t-butyl)benzylmalonate.

Exemplary polyhydric phenols are orcinol, propyl gallate, catechol, resorcinol, 4-octyl-resorcinol, 4-dodecyl-resorcinol, 4-octadecyl-catechol, 4-isooctyl-phloroglucinol, pyrogallol, hexahydroxybenzene, 4-isohexylcatechol, 2,6-di-tertiary-butyl-resorcinol, 2,6-di-isopropyl-phloroglucinol.

Exemplary polyhydric polycyclic phenols are methylene bis-(2,6-di-tertiary-butyl-phenol), 2,2-bis-(4-hydroxy phenyl)-propane, methylene-bis-(p-cresol), 4,4'-benzylidene bis-(2-tertiary-butyl-5-methyl-phenol), 4,4'cyclohexylidene bis-(2-tertiary-butylphenol), 2,2'-methylene-bis-(4-methyl-6-(1'-methylcyclohexyl)-phenol), 2,6-bis-(2'-hydroxy-3'-tertiary-butyl-5'-methylbenzyl)-4-methylphenol, 4,4'-bis-(2-tertiary-butyl-5-methyl-phenol), 2,2'-bis-(4-hydroxy-phenyl)butane, ethylene bis-(p-cresol), 4,4'-oxobis-phenol, 4,4'-oxobis(3-methyl-5-isopropyl-phenol), 4,4'-oxobis-(3-methyl-phenol), 2,2'-oxobis-(4-dodecyl-phenol), 2,2'-oxobis-(4-methyl-5-tertiary-butyl-phenol), 4,4'-thio-bis-phenol; 4,4'-thio-bis-(3-methyl-6-tertiary-butyl-phenol), 2,2'-thio-bis-(4-methyl-6-tertiary-butyl-phenol), 4,4'-n-butylidene-(2-t-butyl-5-methyl-phenol) 2,2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)phenol), 4,4'cyclohexylene bis-(2-tertiary-butyl-phenol), 2,6-bis-(2'-hydroxy-3'-t-butyl-5'-methyl-benzyl)-4-methyl-phenol, 4,4'-oxobis(naphthalene-1,5-diol), 1,3'-bis-(naphthalene-2,5-diol)propane, and 2,2'-butylene bis-(naphthalene-2,7-diol), (3-methyl-5-tert-butyl-4-hydroxyphenyl)-4'-hydroxy-phenyl)propane, 2,2'-methylene-bis-(4-methyl-5-isopropylphenol), 2,2'methylene bis-(5-tert-butyl-4-chlorophenol), (3,5-di-tert-butyl- 4-hydroxyphenyl)-(4'-hydroxyphenyl)ethane, (2-hydroxy-phenyl)-(3',5'-di-tert-butyl-4',4-hydroxyphenyl) ethane, 2,2'-methylene bis-(4-octylphenol); 4,4'-propylene bis-(2-tert-butylphenol), 2,2'-isobutylene bis-(4-nonylphenol), 2,4-bis-(4-hydroxy-3-t-butylphenoxy)-6-(n-octylthio)-1,3,5-triazine, 2,4,6-tris-(4-hydroxy-3-t-butylphenoxy)-1,3,5-triazine, 2,2'-bis-(3-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)thiazole, 2,2'-bis-(3-methyl-5-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)-thiazole, 4,4'-bis-(4-hydroxy-phenyl)pentanoic acid octadecyl ester, cyclopentylene-4,4'-bis-phenol, 2-ethylbutylene-4,4'-bisphenol, 4,4'-cyclooctylene-bis-(2-cyclohexylphenol), β,β-thiodiethanol bis-(3-tert-butyl-4-hydroxyphenoxy acetate), 1,4-butanedio bis-(3-tert-butyl-4-hydroxyphenoxy acetate), pentaerythritoltetra(4-hydroxyphenol propionate), 2,4,4'-tri-hydroxy benzophenone, bis-(2-tert-butyl-3-hydroxy-5-methylphenyl)sulfide, bis-(2-tert-butyl-4-hydroxy-5-methylphenyl)sulfide, bis-(2-tert-butyl-4-hydroxy-5-methyl-phenyl sulfoxide), bis-(3-ethyl-5-tert-butyl-4-hydroxy benzyl)sulfide, bis-(2-hydroxy-4-methyl-6-tert-butyl phenyl)sulfide, 4,4'-bis-(4-hydroxy-phenol)pentanoic acid octadecyl thiopropionate ester, 1,1,3-tris-(2'-methyl-4-hydroxy-5'-tert-butylphenyl)butane, 1,1,3-tris-(1-methyl-3-hydroxy-4-tert-butylphenyl)butane, 1,8-bis-(2-hydroxy-5-methylbenzoyl-n-octane, 2,2'-ethylene-bis-[4'-(3-tert-butyl-4-hydroxyphenyl)-thiazole], 1-methyl-3-(3-methyl-5-tert-butyl-4-hydroxybenzyl)-naphthalene, 2,2'-(2-butene)-bis-(4-methoxy-6-tert-butyl phenol)-bis-[3,3-bis-(4-hydroxy-3-t-butylphenyl)butyric acid]glycol ester, 4,4'-butylidene bis-(6-t-butyl-m-cresol), 1,1,3-tris-(2-methyl-4-hydroxy-5-,t-butylphenyl)butane, 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethyl isocyanurate, 2-octylthio-4,6-di-(4-hydroxy-3,5-di-t-butyl)phenoxy-1,3,5-triazine, 4,4'thiobis(6-t-butyl-m-cresol) and pentaerythritol hydroxyphenyl propionate.

A particularly desirable class of polyhydric polycyclic phenols are the dicyclopentadiene polyphenols, which are of the type: ##STR154## in which R₁ and R₂ are lower alkyl, and can be the same or different, and

n is the number of the groups enclosed by the brackets, and is usually from 1 to about 5. These are described in U.S. Pat. No. 3,567,683, dated Mar. 2, 1971 to Spacht. A commercially available member of this class is Wingstay L, exemplified by dicyclopentadiene tri-(2-tert-butyl-4-methyl-phenol) of the formula: ##STR155##

The polyhydric polycyclic phenols used in the invention can also be condensation products of phenol or alkylphenols with hydrocarbons having a bicyclic ring structure and a double bond or two or more double bonds, such as α-pinene, β-pinene, dipentene, limonene, vinylcyclohexene, dicyclopentadiene, allo-ocimene, isoprene and butadiene. These condensation products are usually obtained under acidic conditions in the form of more or less complex mixtures of monomeric and polymeric compounds. However, it is usually not necessary to isolate the individual constituents. The entire reaction product, merely freed from the acidic condensation catalyst and unchanged starting material, can be used with excellent results. While the exact structure of these phenolic condensation products is uncertain, the Y groups linking the phenolic nuclei all fall into the preferred subgenus 1. For method of preparation, see e.g., U.S. Pat. No. 3,124,555, U.S. Pat. No. 3,242,135 and British Pat. No. 961,504.

In addition, the stabilizer compositions of the invention can include other stabilizers conventionally used as heat and/or light stabilizers for synthetic resins, including polyvalent metal salts of organic acids, organic triphosphites and acid phosphites.

When the stabilizer composition is used in conjunction with a polyvalent metal salt of an organic acid, the organic acid will ordinarily have from about six to about twenty-four carbon atoms. The polyvalent metal can be any metal of Group II of the Periodic Table, such as zinc, calcium, cadmium, barium, magnesium and strontium. The alkali metal salts and heavy metal salts such as lead salts are unsatisfactory. The acid can be any organic non-nitrogenous monocarboxylic acid having from six to twenty-four carbon atoms. The aliphatic, aromatic, alicyclic and oxygen-containing heterocyclic organic acids are operable as a class. By the term "aliphatic acid" is meant any open chain carboxylic acid, substituted, if desired, with nonreactive groups, such as halogen, sulfur and hydroxyl. By the term "alicyclic" it will be understood that there is intended any cyclic acid in which the ring is nonaromatic and composed solely of carbon atoms, and such acids may if desired have inert, nonreactive substituents such as halogen, hydroxyl, alkyl radicals, alkenyl radicals and other carbocyclic ring structures condensed therewith. The oxygen-containing heterocyclic compounds can be aromatic or nonaromatic and can include oxygen and carbon in the ring structure, such as alkyl-substituted furoic acid. The aromatic acids likewise can have nonreactive ring substituents such as halogen, alkyl and alkenyl groups, and other saturated or aromatic rings condensed therewith.

As exemplary of the acids which can be used in the form of their metal salts there can be mentioned the following: hexoic acid, 2-ethylhexoic acid, n-octoic acid, isooctoic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, chlorocaproic acid, hydroxy capric acid, benzoic acid, phenylacetic acid, butyl benzoic acid, ethyl benzoic acid, propyl benzoic acid, hexyl benzoic acid, salicylic acid, naphthoic acid, 1-naphthalene acetic acid, orthobenzoyl benzoic acid, naphthenic acids derived from petroleum, abietic acid, dihydroabietic acid, hexahydrobenzoic acid, and methyl furoic acid.

The water-insoluble salts are preferred, because they are not leached out when the plastic is in contact with water. Where these salts are not known, they are made by the usual types of reactions, such as by mixing the acid, or anhydride with the corresponding oxide or hydroxide of the metal in a liquid solvent, and heating, if necessary, until salt formation is complete.

A variety of organic triphosphites and acid phosphites can be employed, of which the following are exemplary.

The organic triphosphite can be any organic phosphite having three or more organic radicals attached to phosphorus through oxygen. The acid phosphite can be any organic phosphite having one or two organic radicals attached to phosphorus through oxygen. These radicals can be monovalent radicals, in the case of the triphosphites, diphosphites and monophosphites.

The organic triphosphites in which the radicals are monovalent radicals can be defined by the formula: ##STR156## in which R₁, R₂ and R₃ are selected from the group consisting of alkyl, alkenyl, aryl, alkaryl, aralkyl, and cycloalkyl groups having from one to about thirty carbon atoms.

The acid phosphites are defined by the same formula, but one or two of R₁, R₂ and R₃ is hydrogen or a cation of a metal or ammonium.

Also included are the organic triphosphites having a bivalent organic radical forming a heterocyclic ring with the phosphorus of the type: ##STR157## in which R₄ is a bivalent organic radical selected from the group consisting of alkylene, arylene, aralkylene, alkarylene and cycloalkylene radicals having from two to about thirty carbon atoms, and R₅ is a monovalent organic radical as defined above in the case of R₁, R₂ and R₃.

R₅ is hydrogen or a cation, in the case of the acid phosphites.

Also useful organic triphosphites are mixed heterocyclic-open chain phosphites of the type: ##STR158##

More complex triphosphites are formed from trivalent organic radicals, of the type: ##STR159## in which R₆ is a trivalent organic radical of any of the types of R₁ to R₅, inclusive, as defined above.

A particularly useful class of complex triphosphites are the tetraoxadiphosphaspiro undecanes of the formula: ##STR160##

where R₁ and R₂ are selected from the group consisting of aryl, alkyl, aryloxyethyl, alkyloxyethyl, aryloxyethoxyethyl, alkyloxyethoxyethyl and alkyloxypolyethoxyethyl having from about one to about thirty carbon atoms.

In the case of the acid phosphites, one or both of R₁ and R₂ is also hydrogen or a cation.

An especially preferred class of organic triphosphites and acid phosphites have a bicyclic aromatic group attached to phosphorus through oxygen, with no or one or more phenolic hydroxyl groups on either or both of the aromatic rings. These phosphites are characteristics by the formula: ##STR161## in which Ar is a mono or bicyclic aromatic nucleus and m is an integer of from 0 to about 5. Z is one or a plurality of organic radicals as defined above for R₁ to R₆, taken singly or together in sufficient number to satisfy the valences of the two phosphite oxygen atoms.

One or both Z radicals is also hydrogen, in the case of the acid phosphites, and can include additional bicyclic aromatic groups of the type (HO)_(m) --AR.

The cation in the case of acid phosphites can be a metal, such as an alkali metal, for instance, sodium, potassium or lithium; an alkaline earth metal, for instance, barium, calcium, or a nontoxic polyvalent metal, such as magnesium, tin and zinc.

Usually, the triphosphites and acid phosphites will not have more than about sixty carbon atoms.

Exemplary triphosphites are monophenyl di-2-ethylhexyl phosphite, diphenyl mono-2-ethylhexyl phosphite, di-isooctyl monotolyl phosphite, tri-2-ethylhexyl phosphite, phenyl dicyclohexyl phosphite, phenyl diethyl phosphite, triphenyl phosphite, tricresyl phosphite, tri(dimethylphenyl)phosphite, trioctadecyl phosphite, triisooctyl phosphite, tridodecyl phosphite, isooctyl diphenyl phosphite, diisooctyl phenyl phosphite, tri(t-octylphenyl)phosphite, tri(t-nonylphenyl)phosphite, benzyl methyl isopropyl phosphite, butyl dicresyl phosphite, isooctyl di(octylphenyl)phosphite, di(2-ethylhexyl)(isooctylphenyl)phosphite, tri(2-cyclohexylphenyl)phosphite, tri-α-naphthyl phosphite, tri(phenylphenyl)phosphite, tri(2-phenylethyl)phosphite, ethylene phenyl phosphite, ethylene t-butyl phosphite, ethylene isohexyl phosphite, ethylene isooctyl phosphite, ethylene cyclohexyl phosphite, 2-phenoxy-1,3,2-dioxaphosphorinane, 2-butoxy-1,3,2-dioxyphosphorinane, 2-octoxy-5,5-dimethyl-dioxaphosphorinane, and 2-cyclohexyloxy-5,5-diethyl dioxaphosphorinane.

Exemplary pentaerythritol triphosphites are 3,9-diphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane(diphenyl-pentaerythritoldiphosphite), 3,9-di(decyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5,5)-undecane, 3,9-di(isodecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3-phenoxy-9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(methoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di(lauryloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane, 3,9-di-p-tolyloxy-2,4,8,10 tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3,9-di(methoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3-methoxyethyloxy-9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3,9-di(ethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3,9-di(butoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3-methoxyethyloxy-9-butoxyethyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3,9-di(methoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3,9-di(butoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3,9-di(methoxyethoxyethoxyethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane; 3,9-di(methoxy(polyethoxy)ethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5,5)-undecane (where the (polyethoxy)ethyloxy group has an average molecular weight of 350) 3,9-di(methoxy(polyethoxy)ethyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-(5,5)-undecane (where the (polyethoxy)ethyloxy group has an average molecular weight of 550).

Exemplary of the bis aryl triphosphites are: bis(4,4'-thio-bis(2-tertiary butyl-5-methyl-phenol))isooctyl phosphite, mono(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol))di-phenyl phosphite, tri-(4,4'-n-butylidene-bis(2-tertiary-butyl-5-methyl-phenol))phosphite, (4,4'-benzylidene-bis(2-tertiary-butyl-5-methyl-phenol))diphenyl phosphite, isooctyl 2,2'-bis(-parahydroxyphenyl)propane phosphite, decyl 4,4'-n-butylidene-bis(2-tertiary-butyl-5-methylphenol)phosphite, tri-4,4'-thiobis(2-tertiary-butyl-5-methylphenol)phosphite, 2-ethylhexyl-2,2'-methylene-bis(4-methyl-6,1'-methylcyclohexyl)phenol phosphite, tri(2,2'-bis-(para-hydroxyphenyl)propane)phosphite, tri(4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol)phosphite, isooctyl-(2,6-bis(2'-hydroxy-3,5-dinonylbenzyl)-4-nonyl phenyl))phosphite, tetra-tridecyl 4,4'-n-butylidene-bis(2-tertiary butyl-5-methyl phenyl)diphosphite, tetra-isooctyl 4,4'-thiobis(2-tertiary butyl-5-methyl phenyl)diphosphite, 2,2'-methylene-bis(4-methyl 6,1'-methyl cyclohexyl phenyl)polyphosphite, isooctyl-4,4'-isopropylidene-bis-phenyl-polyphosphite, 2-ethylhexyl-2,2'-methylene-bis(4-methyl-6,1'-methyl-cyclohexyl)phenyl triphosphite, tetra-tridecyl-4,4'-oxydiphenyl diphosphite, tetra-n-dodecyl-4,4'-n-butylidene bis(2-tertiary-butyl-5-methylphenyl)diphosphite, tetratridecyl-4,4'-iso-propylidene bisphenyl diphosphite, hexa-tridecyl butane-1,1,3-tris(2'-methyl-5'-tertiary-butylphenyl-4'-)triphosphite.

Exemplary acid phosphites are di(phenyl)phosphite, monophenyl phosphite, mono-(diphenyl)phosphite, dicresyl phosphite, di-(o-isooctylphenyl)phosphite, di(p-ethylhexylphenyl)phosphite, di(p-t-octylphenyl)phosphite, di(dimethylphenyl)phosphite, di-n-butyl phosphite, di-2-ethylhexyl phosphite, mono-2-ethylhexyl phosphite, diisooctyl phosphite, monoisooctyl phosphite, monododecyl phosphite, 2-ethylhexyl phenyl phosphite, 2-ethylhexyl(n-octyphenyl)phosphite, monocyclohexyl phosphite, dicyclohexyl phosphite, di(2-cyclohexyl phenyl)phosphite, di-α-naphthyl phosphite, diphenyl phenyl phosphite, di(diphenyl)phosphite, di-(2-phenyl ethyl)phosphite, dibenzyl phosphite, monobenzyl phosphite, n-butyl cresyl phosphite and didodecyl phosphite, cresyl phosphite, t-octylphenyl phosphite, ethylene phosphite, butyl cresyl phosphite, isooctyl monotolyl phosphite and phenyl cyclohexyl phosphite.

Exemplary of the bis aryl acid phosphites are: bis(4,4'-thio-bis (2-tertiary-butyl-5-methyl-phenol))phosphite, (4,4'-thio-bis(2-tertiary-butyl-5-methyl-phenol))phenyl phosphite, bis(4,4'-n-butylidene-bis(2-tertiary-butyl-5-methyl-phenol))phosphite, mono(4,4'-benzylidene-bis(2-tertiary-butyl-5-methyl-phenol))phosphite, mono(2,2'-bis-(-parahydroxyphenyl)propane)phosphite, mono(4,4'-n-butylidene-bis (-2-tertiary-butyl-5-methyl-phenol) phosphite, bis(4,4'-thiobis(2-tertiary-butyl-5-methylphenol))phosphite, mono-2-ethylhexyl-mono-2,2'methylene-bis(4-methyl-6,1'methylcyclohexyl) phenol phosphite, bis(2,2'-bis-(para-hydroxyphenyl)propane)phosphite, monoisooctyl mono(4,4'thio-bis(2-tertiary-butyl-5-methyl-phenol))phosphite, isooctyl-(2,6-bis(2'-hydroxy-3,5-dinonylbenzyl)-4-nonyl phenyl))phosphite, tri-tridecyl 4,4'-n-butylidene-bis (2-tertiary-butyl-5-methyl phenyl)diphosphite, triisooctyl 4,4'-thiobis(2-tertiary-butyl-5-methyl phenyl)diphosphite, bis (2,2'-methylene-bis(4-methyl-6,1'-methyl cyclohexyl phenyl)phosphite, isooctyl-4,4'-isopropylidene-bis-phenyl phosphite, monophenyl mono(2,2'-methylene-bis(4-methyl-6,1'-methyl-cyclohexyl))triphosphite, di-tridecyl-4,4'-oxydiphenyl diphosphite, di-n-dodecyl-4,4'-n-butylidene bis(2-tertiary-butyl-5-methylphenyl)diphosphite, di-tridecyl-4,4'-isopropylidene bisphenyl diphosphite, tetra-tridecyl butane-1,1,3-tris(2'-methyl-5'-tertiary-butylphenyl-4-)triphosphite.

The hindered heterocyclic amine-alkyl thioalkanoic acid amide stabilizer compositions of the invention are effective stabilizers to enhance the resistance to deterioration due to light and heat of synthetic polymeric materials which are susceptible to such degradation.

The stabilizer systems of the invention are especially effective light stabilizers for olefin polymers such as polyethylene, polypropylene, polybutylene, polypentylene, polyisopentylene, and higher polyolefins.

Olefin polymers on exposure to ultraviolet and actinic light undergo degradation, resulting in embrittlement and discoloration.

The stabilizer systems can be employed with any olefin polymer, including low-density polyethylene, high density polyethylene, polyethylenes prepared by the Ziegler-Natta process, polypropylenes prepared by the Ziegler-Natta process, and by other polymerization methods from propylene, poly(butene-1)poly(pentene-1)poly(3-methylbutene-1)poly(4-methylpentene-1), polystyrene, and mixtures of polyethylene and polypropylene with other compatible polymers, such as mixtures of polyethylene and polypropylene, and copolymers of such olefins, such as copolymers of ethylene, propylene, and butene, with each other and with other copolymerizable monomers, which present the instability problem that is resolved by the stabilizer system of the invention. The term "olefin polymer" encompasses both homopolymers and copolymers.

Polypropylene solid polymer can be defined in a manner to differentiate it from other polyolefins as having a density within the range from 0.86 to 0.91, and a melting point above 150° C. The stabilizer system of the invention is applicable to all such polypropylenes, as distinguished from polypropylenes in the liquid form or in semiliquid or gel-like forms, such as are used as greases and waxes.

The stabilizer system of the invention is applicable to polypropylenes prepared by any of the various procedures, for the molecular weight and tacticity are not factors affecting this stabilizer system. Isotactic polypropylene, available commercially under the trade name PRO-FAX, and having a softening or hot-working temperature of about 350° F., is an example of a sterically regular polypropylene polymer.

Mixtures of polypropylene with other compatible polymers and copolymers of propylene with copolymerizable monomers not reactive with the polypropylene stabilizer combination can also be stabilized, for example, mixtures of polyethylene and polypropylene, and copolymers of propylene and ethylene which have a sufficient amount of propylene to present the instability problem that is resolved by the stabilizer combinations of the invention.

The stabilizer combinations are also effective to enhance the resistance to light degradation of polystyrene; polydienes, such as polybutadiene and polyisoprene; and copolymers of olefins and dienes with other ethylenically and acetylenically unsaturated monomers, such as ethylene vinyl acetate copolymers, styrene-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, synthetic rubbers of all types, such as polychloroprene; polyvinyl halides, including polyvinyl chloride homopolymer, polyvinylidene chloride; and copolymers of vinyl chloride and vinylidene chloride; vinyl chloride and vinyl acetate; vinylidene chloride and vinyl acetate; and other ethylenically unsaturated monomers; polyacetals such as polyoxymethylene and polyoxyethylene; polyesters such as polyethylene glycol-terephthalic acid ester polymers; polyamides such as polyepsiloncaprolactam; polyhexamethylene adipamide and polydecamethylene adipamide; polyurethanes; and epoxy resins.

The synthetic polymer can be in any physical form, including (for example) filaments, yarns, films, sheets, molded articles, latex, and foam.

A sufficient amount of the stabilizer combination is used to improve the resistance of the synthetic polymer to deterioration in physical properties, including, for example, discoloration, reduction in melt viscosity and embrittlement, under the conditions to which the polymer will be subjected. Very small amounts are usually adequate. Amounts within the range from about 0.001 to about 5% total stabilizers by weight of the polymer are satisfactory. Preferably, from 0.01 to 3% is employed, for optimum stabilization.

Inasmuch as all components are solids, the stabilizer systems of the invention are readily rendered in solid particulate form, comprising a blend of

(a) a hindred heterocyclic amine in an amount from about 10 to about 35 parts by weight;

(b) an alkyl thioalkanoic acid amide in an amount of from about 10 to about 35 parts by weight; and, optionally,

(c) a phenolic antioxidant and/or other heat or light stabilizers in an amount of from about 10 to about 35 parts by weight.

The stabilizer compositions of the invention can be employed as the sole stabilizer or in combination with other conventional heat and light stabilizers for the particular synthetic polymer.

Thus, for example, in the case of polyvinyl chloride resins, other polyvinyl chloride resin heat stabilizers can be included, including polyvalent metal fatty acid salts such as barium and cadmium salts of the higher fatty acids; organotin compounds; and epoxy compounds.

When polyolefin resins there can be employed fatty acid salts of polyvalent metals, and the higher fatty acid esters of thiodipropionic acids, such as, for example, dilauryl thiodipropionate.

With polyamide resin compositions, polyamide stabilizers such as copper salts in combination with iodides and/or other phosphorus compounds and salts of divalent manganese can be used.

With synthetic rubbers and acrylonitrile-butadiene-styrene terpolymers, other antioxidants and polyvalent metal salts of the higher fatty acids can be used.

In addition, other conventional additives for synthetic polymers, such as plasticizers, lubricants, emulsifiers, antistatic agents, flame-proofing agents, pigments and fillers, can be employed.

Preferably, the stabilizer system is added to the synthetic polymer in an amount to provide in the polymer from about 0.001 to about 5% of the hindered heterocyclic amine, alkyl thioalkanoic acid amide, and optionally from about 0.001 to about 5% of phenolic antioxidant and/or other heat or light stabilizer.

The stabilizer combination is incorporated in the polymer in suitable mixing equipment, such as a mill or a Banbury mixer. If the polymer has a melt viscosity which is too high for the desired use, the polymer can be worked until its melt viscosity has been reduced to the desired range before addition of the stabilizer. Mixing is continued until the mixture is substantially uniform. The resulting composition is then removed from the mixing equipment and brought to the size and shape desired for marketing or use.

The stabilized polymer can be worked into the desired shape, such as by milling, calendering, extruding or injection molding or fiber-forming. In such operations, it will be found to have a considerably improved resistance to reduction in melt viscosity during the heating, as well as a better resistance to discoloration and embrittlement on ageing and heating.

The following Examples illustrate preferred stabilizer systems and resin compositions of the invention:

EXAMPLES 1 to 11

Polypropylene compositions were prepared using stabilizers of the invention and having the following formulation:

    ______________________________________                                         Ingredient             Parts by Weight                                         ______________________________________                                         Polypropylene          100                                                     Tetrakis [methylene-3-(3,5-di-t-butyl-4-                                       hydroxyphenyl)propionate] methane                                                                     0.1                                                     Hindered heterocyclic amine as listed                                          in Table I             0.2                                                     Alkyl thioalkanoic acid amide as listed                                        in Table I             0.3                                                     ______________________________________                                    

The composition was thoroughly blended in a Brabender Plastograph, and then injection-molded to form sheets 1 mm thick.

Pieces 2.5 cm² were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter, to evaluate light stability, and heated at 160° C. in an oven to evaluate heat stability.

In each test, the time in hours required for the sheet to develop a noticeable discoloration and/or embrittlement was noted as the hours to failure. The results obtained are shown in Table I

                                      TABLE I                                      __________________________________________________________________________                                                          Hours to Failure          Example                                                                             Hindered                                        Light                                                                               Heat                 No.  heterocyclic amine                                                                               Alkyl thioalkanoic acid amide Stability                                                                           Stability            __________________________________________________________________________     Control                                                                        1    None              None                            200                                                                               350                  2    Bis-(2,2,6,6-tetramethyl-4-                                                    piperidinyl)sebacate                                                                             None                            760                                                                               330                  3    None              C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                  210                                                                               830                  4    Bis-(2,2,6,6-tetramethyl-4-                                                    piperidinyl)sebacate                                                                             Dilauryl thiodipropionate       510                                                                               570                  5    2-Hydroxy-4-methoxybenzo-                                                      phenone           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                  680                                                                               850                  6    Bis-(2,2,6,6-tetramethyl-4-                                                    piperidinyl)sebacate(0.5)                                                                        None                            840                                                                               320                  7    None              C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                  210                                                                               870                                         (0.5)                                                   Example                                                                        1    4-Benzoyloxy-2,2,6,6-                                                          tetramethyl piperidine                                                                           C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHNHCOC.sub.2                             H.sub.4 SC.sub.18 H.sub.37    1,120                                                                               920                  2    4-(3,5-Di-t-butyl-4-hydroxy                                                    benzoyloxy)-2,2,6,6-                                                           tetramethyl piperidine                                                                           C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHC.sub.4                                 H.sub.9                       1,090                                                                               940                  3    Bis-(2,2,6,6-tetramethyl-4-                                                    piperidinyl)sebacate                                                                             C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                1,240                                                                               970                  4    tetra-(2,2,6,6-tetramethyl-4-                                                                    C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH.sub.2                                                                1,060                                                                               900                       piperidinyl)-1,3-bis-(aminomethyl)                                             cyclohexane tetraacetate                                                  5    2,2,6,6-Tetramethyl piperidinyl-4- capryloyl hydrozone                                            ##STR162##                   1,020                                                                               880                  6    Tris-(2,2,6,6-tetramethyl-4-                                                   piperidinyl)nitrilo triacetate                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHCH.sub.2NHCO                            C.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                           1,150                                                                               1,040                7    Tris-(2,2,6,6-tetramethyl-4-                                                                     C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.18 H.sub.37                                                                1,020                                                                               940                       piperidinyl)citrate                                                       8    Tris-(2,2,6,6-tetramethyl-4-                                                   piperidinyl)phosphite                                                                            C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHCH.sub.2 NHC                            OC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                          1,060                                                                               940                  9    Tetra-(9-aza-8,8,10,10- tetramethyl-3-ethyl-1,5- dioxaspiro                    [5,5]-3-undecylmethyl). hydrogenated bisphenol A.diphosphite                                      ##STR163##                   1,100                                                                               950                  10   Bis-(9-aza-8,8,10,10-tetramethyl-                                              3-ethyl-1,5-dioxaspiro [5,5]-3-                                                undecylmethyl).hydrogenated                                                    bisphenol A.dicarbonate                                                                          C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.18 H.sub.37                                                                1,280                                                                               1,010                11   Bis-(1,2,2,6,6-pentamethyl-4-                                                  piperidinyl)-2-butyl-2-(3,5-di-                                                tertiarybutyl-4-hydroxybenzyl)                                                 malonate          C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CON(C.sub.                            2 H.sub.5).sub.2              1,100                                                                               950                  __________________________________________________________________________

It is apparent from the above results that the compounds of the invention are superior stabilizers in enhancing the resistance of the polypropylene polymer composition to deterioration in the presence of ultraviolet light and when heated. The synergistic effect is shown upon comparison with the Controls using amine and alkyl thioalkanoic acid amide alone, in like amounts.

EXAMPLES 12 to 20

Ethylene-propylene copolymer compositions of the following formulation were prepared:

    ______________________________________                                         Ingredient             Parts by weight                                         ______________________________________                                         Ethylene-propylene copolymer                                                                          100                                                     2,6-Di-t-butyl-p-cresol                                                                               0.1                                                     Tris(3,5-di-t-butyl-4-hydroxybenzyl)                                           isocyanurate           0.1                                                     Ca-stearate            0.2                                                     Hindered heterocyclic amine as listed                                          in Table II            0.3                                                     Alkyl thioalkanoic acid amide as listed                                        in Table II            0.3                                                     ______________________________________                                    

The compositions were thoroughly blended in a mixer, extruded, and then injection-molded to form sheets 1 mm thick. 2.5 cm² pieces were cut off from the sheet, and light stability in a Weather-O-Meter and heat stability at 160° C. in a Geer-Oven were determined.

The light and heat stability of these sheets was determined by exposure to ultraviolet light and to oven heat.

Pieces 2.5 cm² were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter, and heated at 160° C. in a Geer oven.

In each test the time in hours required for the sheet to develop to noticeable discoloration and/or embrittlement was noted as the hours to failure.

The results obtained are shown in Table II.

                                      TABLE II                                     __________________________________________________________________________                                                            Hours                                                                          to Failure              Ex-                                                    Light                                                                              Heat                ample                                                                              Hindered                                           Stabil-                                                                            Stabil-             No. heterocyclic amine                                                                            Alkyl thioalkanoic acid amide       ity ity                 __________________________________________________________________________     Con-                                                                           trol                                                                           1   None           None                                180 120                 2   Tetra-(2,2,6,6-tetramethyl-4-                                                                 None                                730 110                     piperidinyl)butane tetracar-                                                   boxylate                                                                   3   None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHCH.sub.2NHCOC.su                        b.2 H.sub.4 SC.sub.12 H.sub.25      210 620                 4   Tetra-(2,2,6,6-tetramethyl-4-                                                                 Distearylthiodipropionate           360 310                     piperidinyl)butane tetracar-                                                   boxylate                                                                   5   Tetra-(2,2,6,6-tetramethyl-4-                                                                 None                                800 110                     piperidinyl)butane tetracar-                                                   boxylate (0.6)                                                             6   None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHCH.sub.2NHCOC.su                        b.2 H.sub.4 SC.sub.12 H.sub.25      230 660                                    (0.6)                                                       Ex-                                                                            ample                                                                          12  4-(β-3,5-Di-t-butyl-4-hydroxy-                                                           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                      870 870                     phenyl propionyloxy)-2,2,6,6-                                                  tetramethyl piperidine                                                     13  Bis-(2,2,6,6-tetramethyl-4-                                                                   C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHNHCOC.sub.2                             H.sub.4 SC.sub.18 H.sub.37          920 900                     piperidinyl)sebacate                                                       14  4-Stearoylamino-2,2,6,6- tetramethyl piperidine                                                ##STR164##                         850 810                 15  2,4,6-Tris-(2,2,6,6-tetra-                                                                    C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2 H.sub.4                         NHCOCONHC.sub.2 H.sub.4 NHCOC.sub.2 H.sub.4SC.sub.12                           H.sub.25                            820 890                     methyl-4-piperidinyloxy)-s-                                                    triazine                                                                   16  4-n-Octadecyl-2,2,6,6-                                                                        C.sub.16 H.sub.33 SC.sub.2 H.sub.4 CONHC.sub.6                                                                     850ub.5                                                                            820                     tetramethyl-3,5-diketo                                                         piperazine                                                                 17  Tetra-(2,2,6,6-tetramethyl-                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHCH.sub.2NHCOC.su                        b.2 H.sub.4 SC.sub.12 H.sub.25      920 920                     4-piperidinyl)butane tetra-                                                    carboxylate                                                                18  Bis-(9-aza-8,8,10,10-tetra-                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH.sub.2                                                                      880 850                     methyl-3-ethyl-1,5-dioxaspiro                                                  [5,5]-3-undecylmethyl).penta-                                                  erythritol.diphosphite                                                     19  Bis-(9-aza-8,8,10,10-                                                                         C.sub.20-24 H.sub.41-49 SC.sub.2 H.sub.4 CONHC.sub.6                           H.sub.12 NHCOCONHC.sub.6 H.sub.12 NHCOC.sub.2 H.sub.4                          SC.sub.20-24 H.sub.41-49                                        tetramethyl-3-ethyl-1,5-                           950 930                     dioxaspiro[5,5] -3-                                                            undecylmethyl).hydrogenated                                                    bisphenol A.dicarbonate                                                    20  Bis-(1,2,2,6,6-pentamethyl-                                                                   C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CONHNHCOC.sub.                        2 H.sub.4 SC.sub.12-14 H.sub.25-29  900 890                     4-piperidinyl)-2-butyl-2-                                                      (3,5-di-tertiarybutyl-4-                                                       hydroxybenzyl)malonate                                                     __________________________________________________________________________

It is apparent from the above results that the compounds of the invention are superior stabilizers in enhancing the resistance of the ethylene-propylene copolymer composition to deterioration in the presence of ultraviolet light and heating at 160° C. The synergistic effect is shown upon comparison with the Controls using amine and alkyl thioalkanoic acid amide alone, in like amounts.

EXAMPLES 21 to 29

High density polyethylene compositions were prepared using stabilizers of the invention, and having the following formulation:

    ______________________________________                                         Ingredient            Parts by Weight                                          ______________________________________                                         High-density polyethylene                                                                            100                                                      Ca stearate           0.1                                                      Stearyl-3(3,5-di-t-butyl-4-hydroxyphenyl)                                                            0.1                                                      propionate                                                                     Heterocyclic amine as listed in Table III                                                            0.3                                                      Alkyl thioalkanoic acid amide as listed                                                              0.2                                                      in Table III                                                                   ______________________________________                                    

The stabilizer was blended with the polymer on a two-roll mill and sheets 0.5 mm thick were prepared by compression molding of the blend.

Pieces 2.5 cm² were cut off from the sheets, and exposed to ultraviolet light in a Weather-O-Meter, and heated at 150° C. in a Geer oven.

The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement was noted as hours to failure, and the results are reported in Table III:

                                      TABLE III                                    __________________________________________________________________________                                                             Hours                                                                          to Failure                                                                     Light                                                                              Heat               Exam-                                                                              Hindered                                            Sta-                                                                               Sta-               ple No.                                                                            heterocyclic amine                                                                            Alkyl thioalkanoic acid amide        bility                                                                             bility             __________________________________________________________________________     Con-                                                                           trol                                                                           1   None           None                                 300 160                2   Tris-(2,2,6,6-tetramethyl-4-                                                                  None                                 580 160                    piperidinyl) nitrilo triacetate                                            3   None           C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CONHNHCOC.sub.                        2 H.sub.4 SC.sub.12-14 H.sub.25-29   330 480                4   Tris-(2,2,6,6-tetramethyl-4-                                                                  Distearylthiodipropionate            410 390                    piperidinyl) nitrilo triacetate                                            5   Tris-(2,2,6,6-tetramethyl-4-                                                                  None                                 660 150                    piperidinyl) nitrilo triacetate                                                (0.5)                                                                      6   None           C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CONHNHCOC.sub.                        2 H.sub.4 SC.sub.12-14 H.sub.25-29   340 510                                   (0.5)                                                       Exam-                                                                          ple                                                                            21  Bis-(2,2,6,6-tetramethyl-4- piperidinyl)sebacate                                               ##STR165##                          1,150                                                                              540                22  4-Benzoylamino-2,2,6,6-                                                                       C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.6                                 H.sub.12HCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                       1,030                                                                              530                    tetramethyl piperidine                                                     23  3-n-Octyl-7,7,9,9-tetra-                                                                      C.sub.16 H.sub.33 SC.sub.2 H.sub.4 CONHNHCOC.sub.10                            H.sub.20CONHNHCOC.sub.2 H.sub.4 SC.sub.16 H.sub.33                                                                  1,050                                                                              530                    methyl-1,3,8-triazaspiro                                                       [4,5] decane-2,4-dione                                                     24  N,N'bis-(2,2,6,6-tetra-                                                                       C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.18 H.sub.37                                                                       1,010                                                                              580                    methyl piperidinyl-4-acetyl)                                                   ethylenediamine                                                            25  Tris-(2,2,6,6-tetramethyl-4-                                                                  C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CONHNHCOC.sub.                        2 H.sub.4 SC.sub.12-14 H.sub.25-29   1,260                                                                              570                    piperidinyl) nitrilo triacetate                                            26  Tetra-(2,2,6,6-tetramethyl-4-                                                                 C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                       1,200                                                                              610                    piperidinyl butane tetracar-                                                   boxylate                                                                   27  3,5-Di-t-butyl-4-hydroxybenzyl-                                                               C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CON(C.sub.2                           H.sub.5).sub.2                       1,030                                                                              570                    bis-(2,2,6,6-tetramethyl-4-                                                    piperidyl) phosphonate                                                     28  Bis-(9-aza-8,8,10,10-tetra-                                                                   C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHNHCOC.sub.2                             H.sub.4 SC.sub.18 H.sub.37           1,100                                                                              580                    methyl-3-ethyl-1,5-dioxaspiro                                                  [5,5] 3-undecylmethyl).hydro-                                                  genated bisphenol A.dicar-                                                     bonate                                                                     29  Bis-(1,2,2,6,6-pentamethyl-4-                                                                 C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHNHCOC.sub.2                             H.sub.4SC.sub.2 H.sub.4 CONHNHCOC.sub.2 H.sub.4                                SC.sub.12 H.sub.25                   1,080                                                                              570                    piperidinyl)-2-butyl-2-(3,5-di-                                                tertiarybutyl-4-hydroxybenzyl)                                                 malonate                                                                   __________________________________________________________________________

It is apparent from the above results that the compounds of the invention are superior stabilizers in enhancing the resistance of the polyethylene polymer composition to deterioration in the presence of ultraviolet light and to heat. The synergistic effect is shown upon comparison with the Controls using amine and alkyl thioalkanoic acid amide alone, in like amounts.

EXAMPLES 30 to 37

Ethylene-vinyl acetate copolymer compositions were prepared using stabilizers of the invention and having the following formulation:

    ______________________________________                                         Ingredient            Parts by Weight                                          ______________________________________                                         Ethylene-vinyl acetate copolymer                                                                     100                                                      Montan wax lubricant  0.3                                                      2,6-Di-t-butyl-p-cresol                                                                              0.1                                                      Heterocyclic amine as listed in Table IV                                                             0.3                                                      Alkyl thioalkanoic acid amide as listed in                                                           0.2                                                      table IV                                                                       ______________________________________                                    

The stabilizers were blended with the polymer on a two-roll mill at 120° C., and sheets 1 mm thick were then compression molded at 120° C. from the resulting blend.

Pieces 2.5 cm² were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter for 500 hours. At the start and at the conclusion of the test, the tensile strength of the sheet samples was determined. The results are given in Table IV as % retention of the initially determined tensile strength.

Pieces were also exposed to heat in a Geer oven at 175° C. The time to failure as evidenced by noticeable discoloration and/or embrittlement is reported in hours in Table IV.

                                      TABLE IV                                     __________________________________________________________________________                                                           Reten-                   Ex-                                                   tion of                  am-                                                   tensile                                                                             Hours               ple                                                                               Hindered                                           strength                                                                            failure             No.                                                                               heterocyclic amine                                                                              Alkyl thioalkanoic acid amide     %    (min)               __________________________________________________________________________     Con-                                                                           trol                                                                           1  None             None                              48   45                  2  Bis-(9-aza-8,8,10,10-tetra-                                                                     None                              67   45                     methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   pentaerythritol.diphosphite                                                 3  None             C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHNHCOC.sub.4                             H.sub.8 CONHNHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                               50   60                  4  Bis-(9-aza-8,8,10,10-tetra-                                                                     Butyl-3-(stearylthio)propionate   65   60                     methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   pentaerythritol.diphosphite                                                 5  Bis-(9-aza-8,8,10,10-tetra-                                                                     None                              70   45                     methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   pentaerythritol.diphosphite (0.5)                                           6  None             C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHNHCOC.sub.4                             H.sub.8 CONHNHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                               53   75                                           (0.5)                                                 Ex-                                                                            am-                                                                            ple                                                                            30 4-(β-3,5-Di-t-butyl-4-                                                                     C.sub.30-50 H.sub.61-101 SC.sub.2 H.sub.4 CONHC.sub.2                          H.sub. 4NHCOC.sub.2 H.sub.4 SC.sub.30-50 H.sub.61-101                                                            78   105                    hydroxyphenyl propionyloxy)-                                                   2,2,6,6-tetramethyl piperidine                                              31 N,N' bis-(2,2,6,6-tetramethyl                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4 NHCOCONHC.sub.2 H.sub.4 NHCOC.sub.2 H.sub.4SC.                         sub.12 H.sub.25                   75   120                    4-piperidinyl)oxalamide                                                     32 Tris-(2,2,6,6-tetramethyl-4- piperidinyl)nitrilo triacetate                                      ##STR166##                       82   105                 33 Tetra-(2,2,6,6-tetramethyl-4-                                                                   C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4HCOC.sub.2 H.sub.4 SC.sub.18 H.sub.37                                                                     81   120                    piperidinyl)butane tetracar-                                                   boxylate                                                                    34 Bis(2,4-di-t-butylphenyl)-                                                                      C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHCH.sub.2NHCOC.s                         ub.2 H.sub.4 SC.sub.12 H.sub.25   77   120                    2,2,6,6-tetramethyl-4-                                                         piperidinyl phosphite                                                       35 Bis-(9-aza-8,8,10,10-tetra-                                                                     C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHC.sub.4                                 H.sub.9                           80   120                    methyl-3-ethyl-1,5-dioxaspiro                                                  [5,5]-3-undecylmethyl).penta-                                                  erythritol.diphosphite                                                      36 Bis-(2,2,6,6-tetramethyl-4-                                                                     C.sub.12 H.sub.25 SCH.sub.2 CONHC.sub.2 H.sub.4NHCOCH.                         sub.2 SC.sub.12 H.sub.25          78   90                     piperidinyl)carbonate                                                       37 Bis-(1,2,2,6,6-pentamethyl-4-                                                                   C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONHNHCOC.sub.2                             H.sub.4 SC.sub.18 H.sub.37        82   120                    piperidinyl)-2-butyl-2-(3,5-di-                                                tertiarybutyl-4-hydroxybenzyl)                                                 malonate                                                                    __________________________________________________________________________

It is apparent from the results that the stabilizer compositions in accordance with the invention are superior in enhancing the resistance of the ethylene-vinyl acetate copolymer to deterioration in the presence of ultraviolet light, and at elevated temperature. The synergistic effect is evident from comparison of the examples with the Controls using amine and alkylthioalkanoic acid amide alone in like amounts.

EXAMPLES 38 to 44

A group of polyvinyl chloride resin compositions was prepared having the following formulation:

    ______________________________________                                         Ingredient             Parts by Weight                                         ______________________________________                                         Polyvinyl chloride     100                                                     Dioctylphthalate       50                                                      Ca stearate            1.0                                                     Zn stearate            0.2                                                     Diisodecylphenyl phosphite                                                                            0.5                                                     Heterocyclic amine as listed in Table V                                                               0.2                                                     Alkyl thioalkanoic acid amide as listed                                                               0.05                                                    in Table V                                                                     ______________________________________                                    

This formulation was blended and sheeted off on a two-roll mill to form sheets 1 mm thick. The light resistance of these sheets was then determined by placing strips 1 cm long in a Weather-O-Meter, and exposing them to ultraviolet light. The time in hours was then noted for the sheet to develop a noticeable discoloration and/or embrittlement, indicating deterioration due to oxidation in the presence of ultraviolet light.

The sheets were also heated in a Geer oven at 175° C. to evaluate heat stability, and time in minutes noted for the sheet to develop a noticeable discoloration and/or embrittlement.

The results obtained are given in Table V:

                                      TABLE V                                      __________________________________________________________________________                                                             Time                                                                           to Failure                                                                         Heat                                                                           Sta-               Ex-                                                     Light                                                                              bili-              am-                                                     Resis-                                                                             ty                 ple                                                                               Hindered                                             tance                                                                              (min-              No.                                                                               heterocyclic amine                                                                            Alkyl thioalkanoic acid amide         (hours)                                                                            utes)              __________________________________________________________________________     Con-                                                                           trol                                                                           1  None           None                                  250 60                 2  Bis-(1,2,2,6,6-pentamethyl-                                                                   None                                  450 60                    4-piperidinyl)-2-butyl-2-                                                      (3,5-di-tertiarybutyl-4-                                                       hydroxybenzyl)malonate                                                      3  None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--CH.sub.2                              --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                             260 70                 4  Bis-(1,2,2,6,6-pentamethyl-                                                                   None                                  480 60                    4-piperidinyl)-2-butyl-2-                                                      (3,5-di-tertiarybutyl-4-                                                       hydroxybenzyl)malonate (0.25)                                               5  None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--CH.sub.2                              --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                             260 75                                        (0.25)                                                  Ex-                                                                            am-                                                                            ple                                                                            38 Bis-(2,2,6,6-tetramethyl-4-                                                                   C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONH--C.sub.2                               H.sub.4 --NHCOC.sub.2 H.sub.4 S--C.sub.18 H.sub.37                                                                   800 105                   piperidinyl)sebacate                                                        39 Tetra-(2,2,6,6-tetramethyl-4-                                                                 C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONH--C.sub.4                               H.sub.9                               760 90                    piperidinyl)-1,3-bis-(amino-                                                   methyl cyclohexane                                                             tetraacetate                                                                40 Tris-(2,2,6,6-tetramethyl-4-                                                                  C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--C.sub.2                               H.sub.4 --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                     770 110                   piperidinyl)butane                                                             tricarboxylate                                                              41 Tris-(2,2,6,6-tetramethyl-4-                                                                  C.sub.20-24 H.sub.41-49 SC.sub.2 H.sub.4 CONHC.sub. 6                          H.sub.12 NHCO--CONHC.sub.6 H.sub.12 NHCOC.sub.2 H.sub.4                        SC.sub.20-24 H.sub.41-49              760 100                   piperidinyl)trimellitate                                                    42 Bis-(9-aza-8,8,10,10-tetra-                                                                   C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONH--NHCOC.sub.2                           H.sub.4 SC.sub.18 H.sub.37            790 110                   methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-:undecylmethyl).                                                  pentaerythritol.diphosphite                                                 43 Bis-(9-aza-8,8,10,10-tetra-                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2 H.sub.4                         NHCO--CONCH.sub.2 H.sub.4 NHCOC.sub.2 H.sub.4 --S--C.sub                       .12 H.sub.25                          850 105                   methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   hydrogenated bisphenol A.                                                      dicarbonate                                                                 44 Bis-(1,2,2,6,6-pentamethyl-                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--CH.sub.2                              --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                             830 115                   4-piperidinyl)-2-butyl-2-                                                      (3,5-ddi-tertiarybutyl-4-                                                      hydroxybenzyl)molonate                                                      __________________________________________________________________________

It is apparent from the Controls using amine and alkyl thioalkanoic acid amide alone in like amounts that the stabilizer compositions in accordance with the invention are far superior and display a synergistic effect.

EXAMPLES 45 to 51

Acrylonitrile-butadiene-styrene terpolymer resin compositions were prepared using stabilizer compositions of the invention and having the following formulation:

    ______________________________________                                         Ingredient             Parts by Weight                                         ______________________________________                                         Acrylonitrile-butadiene styrene terpolymer                                                            100                                                     Calcium stearate       0.5                                                     1,1,3-Tris-(2-methyl-4-hydroxy-5-t-                                                                   0.1                                                     butylphenyl)butane                                                             Heterocyclic amine as listed in Table VI                                                              0.4                                                     Alkyl thioalkanoic acid amide as listed                                                               0.2                                                     in Table VI                                                                    ______________________________________                                    

The stabilizers were blended with the resin on a two-roll mill, and sheets 3 mm thick were prepared by compression molding of the resulting blend.

Pieces 2.5 cm² were cut off from the sheets, and subjected to ultraviolet light in a Weather-O-Meter for 800 hours. Tensile strength before and after the test exposure was determined, and the results reported as the percent of tensile strength retained, at the end of this time, in Table VI.

Heat stability was evaluated by heating the sheets at 210° C. under a stress of 50 Kg/cm² for ten minutes, after which the sheets were graded on a scale ranging from 1 to 10 where 1 is colorless and 10 dark brown. The results are shown in Table VI.

                                      TABLE VI                                     __________________________________________________________________________                                                           Tensile                                                                        strength                                                                            Color               Example                                                                             Hindered                                         retained                                                                            of                  No.  heterocyclic amine                                                                            Alkyl thioalkanoic acid amide     %    sheet               __________________________________________________________________________     Control                                                                        1    None           None                              39   8                   2    Bis-(9-aza-8,8,10,10-tetra-                                                                   None                              56   8                        methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   hydrogenated bisphenol A.                                                      dicarbonate                                                               3    None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--CH.sub.2                              --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                         42   4                   4    Bis-(9-aza-8,8,10,10-tetra-                                                                   None                              61   8                        methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   hydrogenated bisphenol A.                                                      dicarbonate (0.6)                                                         5    None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--CH.sub.2                              --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                         43   3                                       (0.6)                                                      Example                                                                        45   4-Benzoyloxy-2,2,6,6-tetra-                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4 NHCO--CONHC.sub.2 H.sub.4 NHCOC.sub.2 H.sub.4                          --S--C.sub.12 H.sub.25            78   2                        methyl piperidine                                                         46   Bis-(2,2,6,6-tetramethyl-4-                                                                   C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CONH--NHCOC.s                         ub.2 H.sub.4 SC.sub.12-14 H.sub.25-29                                                                            80   3                        piperidinyl)sebacate                                                      47   Tris-(2,2,6,6-tetramethyl-4-                                                                  C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONH--C.sub.2                               H.sub.4 --NHCOC.sub.2 H.sub.4 S--C.sub.18 H.sub.37                                                               82   2                        piperidinyl)nitrilo triacetate                                            48   Tetra-(2,2,6,6-tetramethyl-4-                                                                 C.sub.18 H.sub.37 SC.sub.2 H.sub.4 CONH--NHCOC.sub.2                           H.sub.4 SC.sub.18 H.sub.37        81   3                        piperidinyl)butane tetracar-                                                   boxylate                                                                  49   Bis-(9-aza-8,8,10,10-tetra-                                                                   C.sub.16 H.sub.33 SC.sub.2 H.sub.4 CONHNHCO--C.sub.10                          H.sub.20 --CONHNHCOC.sub.2 H.sub.4 SC.sub.16 H.sub.33                                                            78   3                        methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   pentaerythritol.diphosphite                                               50   Bis-(9-aza-8,8,10,10-tetra-                                                                   C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--CH.sub.2                              --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                         83   2                        methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   hydrogenated bisphenol A.                                                      dicarbonate                                                               51   Bis-(1,2,2,6,6-pentamethyl-4-                                                                 C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONH--C.sub.2                               H.sub.4 --NHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                 81   2                        piperidinyl)-2-butyl-2-(3,5-di-                                                tertiarybutyl-4-hydroxybenzyl)                                                 malonate                                                                  __________________________________________________________________________

It is apparent from the data that the combination of heterocyclic amine and alkyl thioalkanoic acid amide is superior to either alone in like amount, showing the synergistic effect of the combination.

EXAMPLES 52 to 60

Polyurethane resin compositions were prepared having the following formulation:

    ______________________________________                                         Ingredient               Parts by Weight                                       ______________________________________                                         Polyurethane resin (U-100; Asahi Denka Kogyo)                                                           100                                                   2,6-Di-t-butyl-p-cresol  0.1                                                   Octyldiphenyl phosphite  0.2                                                   Heterocyclic amine as listed in Table VII                                                               0.5                                                   Alkyl thioalkanoic acid amide as listed                                                                 0.1                                                   in Table VII                                                                   ______________________________________                                    

The stabilizers were blended with the polymer on a two-roll mill at 70° C., and sheets 5 mm thick were prepared by compression molding of the blend at 120° C. Pieces were cut off from the sheets, and light stability evaluated in terms of percent elongation retained after exposure to ultraviolet light in a Fade-O-Meter for fifty hours. Heat stability was determined by heating in a Geer oven at 175° C., and noting the time in minutes for the first noticeable discoloration and/or embrittlement.

The results are shown in Table VII.

                                      TABLE VII                                    __________________________________________________________________________                                                          %      Heat               Example                                                                             Hindered                                        Elongation                                                                            Sta-               No.  heterocyclic amine                                                                            Alkyl thioalkanoic acid amide    retained                                                                              bility             __________________________________________________________________________     Control                                                                        1    None           None                             32      75                2    Tris-(2,2,6,6-tetramethyl-4-                                                                  None                             49      75                     piperidinyl) butane tricar-                                                    boxylate                                                                  3    None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHNHCOC.sub.4                             H.sub.8 CONHNHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                              34      90                4    Tris-(2,2,6,6-tetramethyl-4-                                                                  None                             51      75                     piperidinyl) butane tricar-                                                    boxylate (0.6)                                                            5    None           C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHNHCOC.sub.4                             H.sub.8 CONHNHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.                                                                35     105                                    (0.6)                                                      Example                                                                        52   4-Benyoyloxy-2,2,6,6-                                                                         C.sub.12 H.sub.25 SC.sub.3 H.sub.6 CONHC.sub.2                                 H.sub.4HCOC.sub.3 H.sub.6 SC.sub.12 H.sub.25                                                                    81     120                     tetramethyl piperidine                                                    53   Bis-(1,2,6,6-pentamethyl-                                                                     C.sub.8 H.sub.17 SC.sub.2 H.sub.4 CONHC.sub.18                                 H.sub.37                         78     105                     4-piperidinyl) sebacate                                                   54   2,4,6-Tris-(2,2,6,6-tetra- methyl-4-piperidinylamino)- s-triazine                              ##STR167##                      75     120                55   Bis-(2,2,6,6-tetramethyl-4-                                                                   C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CONHC.sub.2                           H.sub.4 NHCOC.sub.8 H.sub.16     76     105                     piperidinyl-1-oxyl) sebacate                                                                  CONHC.sub.2 H.sub.4 NHCOC.sub.2 H.sub.4 SC.sub.12-14                           H.sub.25-29                                                56   Tris-(2,2,6,6-tetramethyl-4-                                                                  C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHNHCOC.sub.4                             H.sub.8 CONHNHCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                              81     120                     piperidinyl) butane tricar-                                                    boxylate                                                                  57   Tris-(2,2,6,6-tetramethyl-4-                                                                  C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHC.sub.2                                 H.sub.4HCOC.sub.2 H.sub.4 SC.sub.12 H.sub.25                                                                    79     120                     piperidinyl) citrate                                                      58   Phenyl-bis-(2,2,6,6-tetra-                                                                    C.sub.12 H.sub.25 SC.sub.2 H.sub.4 CONHCH.sub.2NHCOC.s                         ub.2 H.sub.4 SC.sub.12 H.sub.25  80     120                     methyl-4-piperidinyl)                                                          phosphinate                                                               59   Bis-(9-aza-8,8,10,10-tetra-                                                                   C.sub.12-14 H.sub.25-29 SC.sub.2 H.sub.4 CONHNHCOC.sub                         .2 H.sub.4 SC.sub.12-14 H.sub.25-29                                                                             84     135                     methyl-3-ethyl-1,5-dioxa-                                                      spiro[5,5]-3-undecylmethyl).                                                   hydrogenated bisphenol A.                                                      dicarbonate                                                               60   Bis-(1,2,2,6,6-pentamethyl-4-                                                                 C.sub.16 H.sub.33 SC.sub.2 H.sub.4 CONHNHCOCHCHCONHNHC                         OC.sub.2 H.sub.4 SC.sub.16 H.sub.33                                                                             82     135                     piperidinyl)-2-butyl-2-(3,5-di-                                                tertiarybutyl-4-hydroxybenzyl)                                                 malonate                                                                  __________________________________________________________________________

The synergistic effect of the combination is apparent from comparison with the Controls using the amine and alkyl thioalkanoic acid amide alone in like amounts. 

Having regard to the foregoing disclosure, the following is claimed as inventive and patentable embodiments thereof:
 1. A light and heat stabilizer composition for synthetic resins comprising:(1) at least one hindered and heterocyclic amine having the formula: ##STR168## wherein: X is a bivalent linking radical including at least one up to four ring carbon atoms completing the ring structure ##STR169## as a heterocyclic ring having from five to seven ring atoms of which at least one is nitrogen and from three to six are carbon; and a substituent selected from the group consisting of Z, O--Z, NH--Z, and ##STR170## wherein Z is the residue of an acid selected from the group consisting of carboxylic acids having from one to thirty carbon atoms, carbonic acid and inorganic oxyacids of phosphorus, silicon and boron and R" is hydrogen or lower alkyl; ═Z₄ wherein Z₄ is a bivalent group selected from the group consisting of: ##STR171## wherein X₄ is hydrogen or methyl; andB is selected from the group consisting of alkyl, epoxy alkyl, alkenyl and cycloalkyl having from one to about eighteen carbon atoms, and ##STR172## in which the alkylene has from one to about ten carbon atoms; R₁ and R₂ are each selected from the group consisting of lower alkyl, and R₁ and R₂ taken together as pentylene (CH₂)₅ ; R₃ and R₄ are each selected from the group consisting of lower alkyl and R₃ and R₄ taken together as one of butylene--(CH₂)₄, pentylene--(CH₂)₅, and CH₂ --C(CH₃)₂ --NH--C(CH₃)₂ --CH₂ --; n is 1 or 2; andwhen n is 1, Y is selected from the group consisting of hydrogen, O., OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and when n is 2, Y is selected from the group consisting of alkylene, alkenylene, alkynylene, cycloalkylene and aralkylene having from one to about thirty carbon atoms; together with (2) at least one alkyl thioalkanoic acid amide having the formula: ##STR173## wherein: R is alkyl having from about four to about fifty carbon atoms;R' is alkylene having from one to about three carbon atoms; R₈ is selected from the group consisting of hydrogen, alkyl and aryl having from about one to about eighteen carbon atoms; and when n is 2 and p is 0, bivalent alkylene and oxyalkylene linked to N at two positions; R₉ is selected from the group consisting of alkylene, dialkylene, cycloalkylene, and arylene having from about one to about twelve carbon atoms; and isocyanurate; R₁₀ is selected from the group consisting of alkylene, alkenylene, thiodialkylene and arylene having from about one to about eighteen carbon atoms; m is 1, 2 or 3; n₁ and n₂ are 0, 1 or 2; p, p₁ and p₂ are 0 or 1; and when p is 1, and n and m are each 1, the sum of m, n and p is three; and q₁, q₂ and q₃ are each 0 or 1; the alkyl thioalkanoic acid amide synergizing the stabilizing effectiveness of the hindered heterocyclic amine.
 2. A light and heat stabilizer composition comprising(1) at least one hindered heterocyclic amine which is a 2,2,6,6-tetrasubstituted piperidine having one of the formulae: ##STR174## wherein: R₁ and R₂ are each selected from the group consisting of lower alkyl, and R₁ and R₂ taken together as pentylene (CH₂)₅ ;R₃ and R₄ are each selected from the group consisting of lower alkyl and R₃ and R₄ taken together or as one of butylene--(CH₂)₄, pentylene--(CH₂)₅, and --CH₂ --C(CH₃)₂ --NH--C(CH₃)₂ --CH₂ --; R₅ and R₆ are selected from the group consisting of hydrogen and lower alkyl; A is >CH-- or ##STR175## wherein R₇ is lower alkyl; n₁ is a number from 1 to 6; Y₂ is selected from the group consisting of hydrogen, O, OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and Z₂ is the residue of an acid selected from the group consisting of carboxylic acids having from one to about thirty carbon atoms, carbonic acid and inorganic oxyacids of phosphorus, silicon and boron; together with (2) at least one alkyl thioalkanoic acid amide having the formula: ##STR176## wherein: R is alkyl having from about four to about fifty carbon atoms;R' is alkylene having from one to about three carbon atoms; R₈ is selected from the group consisting of hydrogen, alkyl and aryl having from about one to about eighteen carbon atoms; and when n is 2 and p is 0, bivalent alkylene and oxyalkylene linked to N at two positions; R₉ is selected from the group consisting of alkylene, dialkylene, cycloalkylene, and arylene having from about one to about twelve carbon atoms; and isocyanurate; R₁₀ is selected from the group consisting of alkylene, alkenylene, thiodialkylene and arylene having from about one to about eighteen carbon atoms; m is 1, 2 or 3; n₁ and n₂ are 0, 1 or 2; p, p₁ and p₂ are 0 or 1; and when p is 1, and n and m are each 1, the sum of m, n and p is three; and q₁, q₂ and q₃ are each 0 or 1; the alkyl thioalkanoic acid amide synergizing the stabilizing effectiveness of the hindered heterocyclic amine.
 3. A light and heat stabilizer composition according to claim 1 in which the hindered heterocyclic amine has the formula: ##STR177## in which Y₃ is selected from the group consisting of hydrogen, O., OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; andZ₃ is the residue of an acid selected from the group consisting of carboxylic acids having from one to about thirty carbon atoms, carbonic acid, and inorganic oxyacids of phosphorus, silicon, and boron.
 4. A light and heat stabilizer composition according to claim 1 in which the hindered heterocyclic amine has the formula: ##STR178## wherein Z₄ is a bivalent group selected from the group consisting of ##STR179##
 5. A light and heat stabilizer composition comprising(1) at least one hindered heterocyclic amine having the formula: ##STR180## in which Y₄ is hydrogen or methyl;X₄ is hydrogen or methyl; and B is selected from the group consisting of alkyl, epoxy alkyl, alkenyl and cycloalkyl having from one to about eighteen carbon atoms, and alkylene ##STR181## in which the alkylene has from one to about ten carbon atoms; together with (2) at least one alkyl thioalkanoic acid amide having the formula: ##STR182## wherein: R is alkyl having from about four to about fifty carbon atoms;R' is alkylene having from one to about three carbon atoms; R₈ is selected from the group consisting of hydrogen, alkyl and aryl having from about one to about eighteen carbon atoms; and when n is 2 and p is 0, bivalent alkylene and oxyalkylene linked to N at two positions; R₉ is selected from the group consisting of alkylene, dialkylene, cycloalkylene, and arylene having from about one to about twelve carbon atoms; and isocyanurate; R₁₀ is selected from the group consisting of alkylene, alkenylene, thiodialkylene and arylene having from about one to about eighteen carbon atoms; m is 1, 2 or 3; n₁ and n₂ are 0, 1 or 2; p, p₁ and p₂ are 0 or 1; and when p is 1, and n and m are each 1, the sum of m, n and p is three; and q₁, q₂ and q₃ are each 0 or 1; the alkyl thioalkanoic acid amide synergizing the stabilizing effectiveness of the hindered heterocyclic amine.
 6. A light and heat stabilizer composition comprising(1) at least one hindered heterocyclic amine having the formula: ##STR183## in which R₈ is hydrogen or alkyl having from one to about six carbon atoms;p₃ is an even number from 2 to 6; and Z₅ is the residue of an acid selected from the group consisting of carboxylic acids having from one to about thirty carbon atoms, carbonic acid, and inorganic oxyacids of phosphorus, silicon and boron; together with (2) at least one alkyl thioalkanoic acid amide having the formula: ##STR184## wherein: R is alkyl having from about four to about fifty carbon atoms;R' is alkylene having from one to about three carbon atoms; R₈ is selected from the group consisting of hydrogen, alkyl and aryl having from about one to about eighteen carbon atoms; and when n is 2 and p is 0, bivalent alkylene and oxyalkylene linked to N at two positions; R₉ is selected from the group consisting of alkylene, dialkylene, cycloalkylene, and arylene having from about one to about twelve carbon atoms; and isocyanurate; R₁₀ is selected from the group consisting of alkylene, alkenylene, thiodialkylene and arylene having from about one to about eighteen carbon atoms; m is 1, 2 or 3; n₁ and n₂ are 0, 1 or 2; p, p₁ and p₂ are 0 or 1; and when p is 1, and n and m are each 1, the sum of m, n and p is three; and q₁, q₂ and q₃ are each 0 or 1; the alkyl thioalkanoic acid amide synergizing the stabilizing effectiveness of the hindered heterocyclic amine.
 7. A light and heat stabilizer composition according to claim 1 in which X is alkylene having from two to four carbon atoms.
 8. A light and heat stabilizer composition according to claim 1 in which X is B--A<, wherein A is alkylene having from two to four carbon atoms completing the ring structure and B is a carboxylic acid ester group.
 9. A light and heat stabilizer composition according to claim 1 in which X is ##STR185## wherein A is alkylene completing the ring structure, B is a carboxylic acid ester group and C is a phenolic group.
 10. A light and heat stabilizer composition according to claim 1 in which X is alkylene substituted with an amide group.
 11. A light and heat stabilizer composition according to claim 1 in which X is alkylene substituted with a phenolic group.
 12. A light and heat stabilizer composition comprising(1) at least one hindered and heterocyclic amine having the formula: ##STR186## wherein A is alkylene completing the ring structure;X is a bivalent linking radical including at least one up to four ring carbon atoms completing the ring structure ##STR187## as a heterocyclic ring having from five to seven ring atoms of which at least one is nitrogen and from three to six are carbon; R₁ and R₂ are each selected from the group consisting of lower alkyl, and R₁ and R₂ taken together as pentylene (CH₂)₅ ; R₃ and R₄ are each selected from the group consisting of lower alkyl and R₃ and R₄ taken together as one of butylene--(CH₂)₄, pentylene--(CH₂)₅, and CH₂ --C(CH₃)₂ --NH--C(CH₃)₂ --CH₂ --; n is 1 or 2; and when n is 1, Y is selected from the group consisting of hydrogen, O., OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and when n is 2, Y is selected from the group consisting of alkylene, alkenylene, alkynylene, cycloalkylene and aralkylene having from one to about thirty carbon atoms; together with (2) at least one alkyl thioalkanoic acid amide having the formula: ##STR188## wherein: R is alkyl having from about four to about fifty carbon atoms;R' is alkylene having from one to about three carbon atoms; R₈ is selected from the group consisting of hydrogen, alkyl and aryl having from about one to about eighteen carbon atoms; and when n is 2 and p is 0, bivalent alkylene and oxyalkylene linked to N at two positions; R₉ is selected from the group consisting of alkylene, dialkylene, cycloalkylene, and arylene having from about one to about twelve carbon atoms; and isocyanurate; R₁₀ is selected from the group consisting of alkylene, alkenylene, thiodialkylene and arylene having from about one to about eighteen carbon atoms; m is 1, 2 or 3; n₁ and n₂ are 0, 1 or 2; p, p₁ and p₂ are 0 or 1; and when p is 1, and n and m are each 1, the sum of m, n and p is three; and q₁, q₂ and q₃ are each 0 or 1; the alkyl thioalkanoic acid amide synergizing the stabilizing effectiveness of the hindered heterocyclic amine.
 13. A light and heat stabilizer composition according to claim 1 in which X is alkylene substituted with a phosphite ester group.
 14. A light and heat stabilizer composition according to claim 1 in which m is 1, n is 2, R₈ is H, and p is
 0. 15. A light and heat stabilizer composition according to claim 1 in which m is 1, n is 2, and R₈ is H and one R₈ is alkyl, and p is
 0. 16. A light and heat stabilizer composition according to claim 1 in which R' is ethylene.
 17. A light and heat stabilizer composition according to claim 1 in which m is 1, n is 1, p is 1, p₁ and p₂ are 0, and q₁ is
 1. 18. A light and heat stabilizer composition according to claim 1 in which m is 1, n₁ and n₂ are 1, p is 1, p₁ and p₂ are 0, and q is
 0. 19. A light and heat stabilizer composition according to claim 1 in which m is 1, n₁ and n₂ are each 1, p, p₁ and p₂ are each 1, and q₁, q₂ and q₃ are each
 0. 20. A light and heat stabilizer composition according to claim 1 in which m is 1, n₁ and n₂ are each 1, p, p₁ and p₂ are each 1, q₂ is 1 and q₁ and q₃ are each
 0. 21. An olefin polymer composition having improved resistance to deterioration comprising an olefin polymer selected from the group consisting of polymers of alpha-olefins having from two to six carbon atoms and polystyrene, and a compound in accordance with claim
 1. 22. An olefin polymer composition in accordance with claim 21 wherein the polyolefin is polypropylene.
 23. An olefin polymer composition in accordance with claim 21 wherein the polyolefin is polyethylene.
 24. An ethylene propylene copolymer composition having improved resistance to deterioration comprising an ethylene propylene copolymer and a compound in accordance with claim
 1. 